CN110139893B

CN110139893B - Prepreg, laminate, metal foil-clad laminate, printed wiring board, and multilayer printed wiring board

Info

Publication number: CN110139893B
Application number: CN201780081386.5A
Authority: CN
Inventors: 滨岛知树; 山口翔平; 久保孝史; 伊藤环; 志贺英祐
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-12-28
Filing date: 2017-12-27
Publication date: 2021-11-19
Anticipated expiration: 2037-12-27
Also published as: TWI725387B; JP2019048990A; JP6424992B1; KR20190026953A; TW201920399A; JPWO2018124158A1; TWI656151B; KR102026591B1; WO2018124158A1; CN114196204B; TW201831572A; JP6681052B2; CN114196204A; CN110139893A

Abstract

The prepreg of the present invention comprises a thermosetting resin, a filler, and a base material, and is intended to provide a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board which do not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless board. A cured product obtained by thermally curing the prepreg at 230 ℃ for 100 minutes satisfies the following formulas (1) to (5); e '(200 ℃)/E' (30 ℃) is less than or equal to 0.90 … (1) E '(260 ℃)/E' (30 ℃) is less than or equal to 0.85 … (2) E '(330 ℃)/E' (30 ℃) is less than or equal to 0.80 … (3) E 'max/E' (30 ℃) is less than or equal to 3.0% … (4) E 'min/E' (30 ℃) is more than or equal to 0.5% … (5) (E ': storage modulus, E': loss modulus).

Description

Prepreg, laminate, metal foil-clad laminate, printed wiring board, and multilayer printed wiring board

Technical Field

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

Background

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

One of the measures against this problem is to reduce the thermal expansion of the insulating layer used in the printed wiring board. This is a method of suppressing warpage by making the thermal expansion coefficient of a printed wiring board close to that of a semiconductor element, and is now under active study (for example, see patent documents 1 to 3).

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

Documents of the prior art

Patent document

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

Patent document 2: japanese patent No. 3173332

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

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

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

Disclosure of Invention

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

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

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition that can achieve a higher storage modulus under heat and a higher retention rate of elastic modulus in a cured product of a prepreg is effective for the warpage behavior of a printed circuit board for semiconductor plastic encapsulation, but the present invention is not limited thereto. Further, the present inventors have conducted intensive studies and as a result, have found that the above-mentioned problems can be solved by satisfying a predetermined condition range with respect to a physical property parameter relating to a specific mechanical property in a cured product obtained by thermally curing a prepreg. Namely, the following are found: the above problems can be solved by satisfying a specific condition range in the hot storage modulus and loss modulus of a cured product obtained by thermally curing a prepreg, and the present invention has been completed.

Namely, the present invention is as follows.

〔1〕

A prepreg, comprising: a thermosetting resin, a filler and a base material,

a cured product obtained by thermally curing the prepreg at 230 ℃ for 100 minutes satisfies the numerical range of physical property parameters relating to mechanical properties represented by the following formulas (1) to (5),

E’(200℃)/E’(30℃)≤0.90…(1)

E’(260℃)/E’(30℃)≤0.85…(2)

E’(330℃)/E’(30℃)≤0.80…(3)

E”max/E’(30℃)≤3.0％…(4)

E”min/E’(30℃)≥0.5％…(5)

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

〔2〕

The prepreg according to [ 1], which further satisfies mechanical properties represented by the following formula (6A),

E’(30℃)≤30GPa…(6A)

(wherein E' represents the storage modulus of the cured product at the temperature shown in parentheses.).

〔3〕

The prepreg according to [ 1] or [ 2], wherein the substrate is a glass substrate.

〔4〕

The prepreg according to [ 3 ], wherein the glass substrate is composed of fibers of 1 or more kinds of glass selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.

〔5〕

A laminated sheet comprising at least 1 or more of the prepregs according to any one of [ 1] to [ 4 ] laminated.

〔6〕

A metal-clad laminate comprising:

at least 1 or more sheets of the prepreg according to any one of [ 1] to [ 4 ] stacked, and

and a metal foil disposed on one or both surfaces of the prepreg.

〔7〕

A printed circuit board, having:

an insulating layer formed from the prepreg according to any one of [ 1] to [ 4 ], and

and a conductor layer formed on the surface of the insulating layer.

〔8〕

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

the plurality of insulating layers includes: a 1 st insulating layer formed from the prepreg according to any one of [ 1] to [ 4 ] in which at least 1 sheet is stacked, and a 2 nd insulating layer formed from the prepreg according to any one of [ 1] to [ 4 ] in which at least 1 sheet is stacked in one-side direction of the 1 st insulating layer,

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

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board, which can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless substrate, can be provided.

Drawings

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

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

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

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

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

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

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

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

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

Detailed Description

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

[ prepreg ]

The prepreg of the present embodiment contains: a base material, and a resin composition described later impregnated or applied to the base material. The prepreg production method can be carried out by a conventional method, and is not particularly limited. For example, the prepreg of the present embodiment can be produced by impregnating or applying the resin composition of the present embodiment to a substrate, and then semi-curing (B-staging) the resin composition by heating the resin composition in a dryer at 100 to 200 ℃ for 1 to 30 minutes.

In addition, the prepreg of the present embodiment satisfies the numerical range of the physical property parameters relating to the mechanical properties shown in the following expressions (1) to (5), preferably satisfies the numerical range of the physical property parameters relating to the mechanical properties shown in the following expressions (1A) to (5A), in a cured product obtained by heat curing at 230 ℃ for 100 minutes.

E’(200℃)/E’(30℃)≤0.90…(1)

E’(260℃)/E’(30℃)≤0.85…(2)

E’(330℃)/E’(30℃)≤0.80…(3)

E”max/E’(30℃)≤3.0％…(4)

E”min/E’(30℃)≥0.5％…(5)

0.40≤E’(200℃)/E’(30℃)≤0.90…(1A)

0.40≤E’(260℃)/E’(30℃)≤0.85…(2A)

0.40≤E’(330℃)/E’(30℃)≤0.80…(3A)

0.5％≤E”max/E’(30℃)≤3.0％…(4A)

3.0％≥E”min/E’(30℃)≥0.5％…(5A)

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

Conventionally, regarding the warpage behavior of a printed circuit board, a resin composition that can achieve a higher storage modulus under heat and a higher retention rate of elastic modulus in a cured product of a prepreg has been considered effective, but is not limited thereto, and the numerical value of the physical property parameter relating to the mechanical properties of a cured product obtained by heat curing the prepreg at 230 ℃ for 100 minutes is within the range of the above-described formulae (1) to (5), preferably formulae (1A) to (5A), whereby the glass transition temperature (Tg) can be sufficiently increased and the warpage amount of a laminate, a metal foil-clad laminate, a printed circuit board, and particularly a multilayered coreless substrate itself can be sufficiently reduced.

In other words, by setting the numerical value of the physical property parameter relating to the mechanical property of the cured product obtained by heat-curing the prepreg at 230 ℃ for 100 minutes to fall within the ranges of the above-described formulae (1) to (5), preferably formulae (1A) to (5A), it is possible to adequately reduce the warpage (achieve low warpage) of the printed wiring board (particularly, the multilayer coreless substrate) without having a clear glass transition temperature (no Tg). That is, it can be said that the expressions (4) and (5), preferably the expressions (4A) and (5A), which satisfy the loss modulus, have the same meaning as the absence of a clear glass transition temperature (Tg) (no Tg), but when the cured product satisfies only the expressions (4) and (5), preferably the expressions (4A) and (5A), and does not satisfy the expressions (1) to (3), preferably the expressions (1A) to (3A), the loss modulus itself is small and is difficult to elongate, but when the cured product is formed into a printed wiring board, the degree of difficulty in elongation is troublesome, and it is difficult to achieve low warpage. On the other hand, when the cured product satisfies not only the formulae (4) and (5), preferably the formulae (4A) and (5A), but also the formulae (1) to (5), preferably the formulae (1A) to (5A), there is a tendency that elongation is difficult due to no Tg and low warpage of the printed wiring board is easily achieved.

Further, the prepreg of the present embodiment preferably satisfies the mechanical properties shown by the following formula (6A), and more preferably satisfies the mechanical properties shown by the following formula (6) and/or formula (6B).

E’(30℃)≤30GPa…(6A)

E’(30℃)≤25GPa…(6)

1GPa≤E’(30℃)…(6B)

In the formula, E' represents the storage modulus of the cured product at the temperature shown in parentheses. That is, the prepreg of the present embodiment preferably has an E' (30 ℃ C.) value of 30GPa or less, more preferably 25GPa or less. The lower limit of E' (30 ℃ C.) is not particularly limited, but is preferably 1GPa or more.

The mechanical properties of a cured product obtained by thermally curing the prepreg at 230 ℃ for 100 minutes are within the range of the formula (6), whereby the warpage of the multilayer coreless substrate in particular can be further reduced.

The method for measuring the mechanical properties (storage modulus E' and loss modulus E ") of the cured product of the prepreg is not particularly limited, and can be measured, for example, by the following method. That is, copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of prepreg, and the pressure was set to 30kgf/cm²Then, the laminate was laminated and molded (heat-cured) at 230 ℃ for 100 minutes to obtain a copper clad laminate having a predetermined insulating layer thickness. Next, the obtained copper clad laminate was cut into a size of 5.0mm × 20mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. The mechanical properties (storage modulus E' and loss modulus E ") were measured by the DMA method using this measurement sample according to JIS C6481 using a dynamic viscoelasticity analyzer (TA Instruments). In this case, an average value of n equal to 3 can be obtained.

The content of the resin composition (including the filler (H) described later) in the prepreg is preferably 30 to 90 vol%, more preferably 35 to 85 vol%, and still more preferably 40 to 80 vol% based on the total amount of the prepreg. When the content of the resin composition is within the above range, moldability tends to be further improved.

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

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

[ resin composition ]

The resin composition of the present embodiment used in the prepreg is not particularly limited as long as it contains a thermosetting resin and a filler, and for example, a composition containing a maleimide compound (a), an allyl group-containing compound (B), and an epoxy resin (C) containing a bisphenol a structural unit and a hydrocarbon structural unit can be appropriately selected, and can realize a numerical range of physical property parameters relating to mechanical properties represented by the formulas (1) to (5), preferably the formulas (1A) to (5A). Laminates, metal foil-clad laminates, printed wiring boards, and particularly multilayer coreless substrates, which use prepregs comprising such a resin composition and a base material, tend to be able to sufficiently reduce the amount of warpage due to heating such as reflow soldering.

[ Maleimide Compound (A) ]

The maleimide compound (A) is not particularly limited as long as it is a compound having 1 or more maleimide groups in the molecule, examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, maleimide compounds represented by the following formula (7), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Among them, at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and a maleimide compound represented by the following formula (7) is preferable, and a maleimide compound represented by the following formula (7) is particularly preferable. By containing such a maleimide compound (a), the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance and the glass transition temperature (Tg) tend to be further improved.

Here, in formula (7), R₅Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (7), n₁Represents an integer of 1 or more, preferably an integer of 10 or less, more preferably an integer of 7 or less.

The content of the maleimide compound (a) is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, still more preferably 25 to 50 parts by mass, particularly preferably 35 to 50 parts by mass, and still more preferably 35 to 45 parts by mass, per 100 parts by mass of the resin solid content. When the content of the maleimide compound (a) is in the above range, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

[ allyl group-containing Compound (B) ]

The allyl group-containing compound (B) is not particularly limited as long as it has 1 or more allyl groups in the molecule, and may further contain a reactive functional group other than allyl groups. The reactive functional group other than the allyl group is not particularly limited, and examples thereof include an isocyanate group (Cyanate group), a hydroxyl group, an epoxy group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric acid group. Among them, at least 1 selected from the group consisting of Cyanate group (Cyanate group), hydroxyl group, and epoxy group is preferable, and Cyanate group (Cyanate group) is more preferable. The resin composition containing a hydroxyl group, a Cyanate group (Cyanate group), and an epoxy group tends to have high flexural strength and flexural modulus, low dielectric constant, high glass transition temperature (high Tg), low thermal expansion coefficient, and further improved thermal conductivity.

The allyl group-containing compound (B) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the allyl group-containing compound (B) having 2 or more kinds of reactive functional groups other than allyl groups is used in combination, the reactive functional groups other than allyl groups may be the same or different. Among them, the allyl group-containing compound (B) preferably contains an allyl group-containing compound whose reactive functional group is a cyanate group and an allyl group-containing compound whose reactive functional group is an epoxy group. By using such an allyl group-containing compound (B) in combination, the flexural strength, flexural modulus, glass transition temperature (Tg), and thermal conductivity tend to be further improved.

Among the above, as the allyl group-containing compound (B), an allyl group-containing compound having a reactive functional group other than an allyl group and/or the alkenyl-substituted nadiimide compound (E) described later is preferably used. By using such an allyl group-containing compound (B), the glass transition temperature (Tg), the thermal expansion coefficient, and the thermal conductivity tend to be improved.

Further, as the allyl group-containing compound (B), the allyl phenol derivative (D) and/or the alkenyl-substituted nadiimide compound (E) described later are particularly preferably used. By using such an allyl group-containing compound (B), the glass transition temperature (Tg), the thermal expansion coefficient, and the thermal conductivity tend to be further improved.

The content of the allyl group-containing compound (B) is preferably 1 to 90 parts by mass, more preferably 10 to 80 parts by mass, still more preferably 20 to 75 parts by mass, and particularly preferably 25 to 40 parts by mass, per 100 parts by mass of the resin solid content. When the content of the allyl group-containing compound (B) is in the above range, flexibility, flexural strength, flexural modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and copper foil peel strength of the obtained cured product tend to be further improved.

(allylphenol derivative (D))

The allyl phenol derivative (D) is not particularly limited as long as it is a compound in which an allyl group and a phenolic hydroxyl group are directly bonded to an aromatic ring and a derivative thereof, and examples thereof include a bisphenol in which a hydrogen atom of an aromatic ring is substituted with an allyl group, a modified bisphenol compound in which a hydrogen atom of an aromatic ring is substituted with an allyl group, and a phenolic hydroxyl group is modified with a reactive functional group other than a hydroxyl group among the above reactive functional groups other than an allyl group, more specifically, a compound represented by the following formula (8), and more specifically, a bisallylbisphenol a, a cyanate ester compound of a diallylbisphenol a, and a diallylbisphenol a type epoxy compound.

In formula (8), Ra each independently represents a reactive substituent other than allyl.

The compound represented by formula (8) is not particularly limited, and examples thereof include a compound represented by formula (8a) and/or a compound represented by formula (8 b). By using such an allylphenol derivative (D), the flexural strength, flexural modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and copper foil peel strength tend to be further improved.

The bisphenol is not particularly limited, and examples thereof include bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Among them, bisphenol A is preferred.

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

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

The content of the allyl phenol derivative (D) is suitably in the range based on the content of the above allyl group-containing compound (B).

(alkenyl-substituted nadimide compound (E))

The alkenyl-substituted nadimide compound (E) is not particularly limited as long as it has 1 or more alkenyl-substituted nadimide groups in the molecule. Among them, a compound represented by the following formula (9) is preferable. By using such an alkenyl-substituted nadimide compound (E), the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

In the formula (9), R₁Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R₂Represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (10) or (11).

In the formula (10), R₃Represents methylene, isopropylidene, or, CO, O, S, or SO₂The substituents shown.

In the formula (11), R₄Each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.

The alkenyl-substituted nadiimide compound (E) is more preferably a compound represented by the following formula (12) and/or (13). By using such an alkenyl-substituted nadimide compound (E), the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

The alkenyl-substituted nadimide compound (E) may be a commercially available compound. The commercially available substance is not particularly limited, and examples thereof include BANI-M (a compound represented by formula (12) and manufactured by PELLE PETROL CO., LTD.), BANI-X (a compound represented by formula (13) and manufactured by PELLE PETROL CO., LTD.), and the like. These may be used in 1 kind or in combination of 2 or more kinds.

The content of the alkenyl-substituted nadiimide compound (E) is preferably 20 to 50 parts by mass, and more preferably 20 to 35 parts by mass, per 100 parts by mass of the resin solid content. Further, the total content of the allyl phenol derivative (D) and the alkenyl-substituted nadiimide compound (E) is preferably 20 to 50 parts by mass, and more preferably 35 to 45 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the alkenyl-substituted nadimide compound (E) is in the above range, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

[ epoxy resin (C) comprising bisphenol A structural units and hydrocarbon structural units ]

The epoxy resin (C) containing a bisphenol a structural unit and a hydrocarbon structural unit is not particularly limited as long as it is a compound having 1 or more bisphenol a structural units and 1 or more hydrocarbon structural units in the molecule. Among them, a compound represented by the following formula (14) is preferable. By using the epoxy resin (C) containing the bisphenol a structural unit and the hydrocarbon structural unit, the storage modulus E' of the obtained cured product when heated tends to be a value suitable for warpage suppression.

Here, in formula (14), R₁And R₂Each independently represents a hydrogen atom or a methyl group, R₃～R₆Each independently represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, and X represents an ethyleneoxyethyl group or a di (ethylene) groupOxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or alkylene group having 2 to 15 carbon atoms, and n represents a natural number.

The epoxy resin (C) containing a bisphenol a structural unit and a hydrocarbon structural unit may be a commercially available one. The commercially available substance is not particularly limited, and examples thereof include EPICLON EXA-4850-150 (a compound having a structure represented by formula (14) manufactured by DIC), EPICLON EXA-4816 (a compound wherein X in formula (14) manufactured by DIC) and the like. These may be used in 1 kind or in combination of 2 or more kinds.

The content of the epoxy resin (C) containing a bisphenol a structural unit and a hydrocarbon structural unit is preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 20 parts by mass, per 100 parts by mass of the resin solid content. When the content of the epoxy resin (C) containing a bisphenol a structural unit and a hydrocarbon structural unit is in the above range, the storage modulus E' of the obtained cured product during heating tends to be a value suitable for suppressing warpage.

[ cyanate ester compound (F) ]

The resin composition of the present embodiment may further contain a cyanate ester compound (F). The cyanate ester compound (F) is not particularly limited as long as it is a cyanate ester compound other than the above allyl phenol derivative (D), and examples thereof include naphthol aralkyl type cyanate ester represented by the following formula (15), novolak type cyanate ester represented by the following formula (16), biphenyl aralkyl type cyanate ester, bis (3, 5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1,3, 5-tricarboxyylbenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 6-dicyanobenzene, 1, 8-dicyanobenzene, 2, 6-dicyanobenzene, 2, 7-dicyanobenzene, 1,3, 6-tricyanonaphthalene, 4,4 '-dicyanoylbiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, and 2, 2' -bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters, and the like. These cyanate ester compounds (F) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the formula (15), R₆Each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In the formula (15), n₂Represents an integer of 1 or more. n is₂The upper limit value of (2) is usually 10, preferably 6.

In the formula (16), R₇Each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In the formula (16), n₃Represents an integer of 1 or more. n is₃The upper limit value of (b) is usually 10, preferably 7.

Among these, the cyanate ester compound (F) preferably contains 1 or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (15), novolac type cyanate ester represented by formula (16), and biphenyl aralkyl type cyanate ester, and more preferably contains 1 or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (15) and novolac type cyanate ester represented by formula (16). By using such a cyanate ester compound (F), a cured product having more excellent flame retardancy, higher curability, and a lower thermal expansion coefficient tends to be obtained.

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

The phenolic resin to be a raw material of the cyanate ester compound (F) is not particularly limited, and examples thereof include naphthol aralkyl type phenolic resins, novolac type phenolic resins, and biphenyl aralkyl type phenolic resins represented by the following formula (17).

In the formula (17), R₈Each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In the formula (17), n₄Represents an integer of 1 or more. n is₄The upper limit value of (2) is usually 10, preferably 6.

The naphthol aralkyl type phenol resin represented by the formula (17) can be obtained by condensing a naphthol aralkyl resin with cyanic acid. The naphthol aralkyl type phenol resin is not particularly limited, and examples thereof include those obtained by the reaction of a naphthol such as α -naphthol and β -naphthol with a benzene such as p-xylylene glycol, α' -dimethoxyp-xylene, and 1, 4-bis (2-hydroxy-2-propyl) benzene. The naphthol aralkyl type cyanate ester may be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above with cyanic acid.

The content of the cyanate ester compound (F) is preferably 0.5 to 45 parts by mass, more preferably 10 to 45 parts by mass, more preferably 15 to 45 parts by mass, and still more preferably 20 to 35 parts by mass, per 100 parts by mass of the resin solid content. When the content of the cyanate ester compound is in the above range, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.

[ epoxy Compound (G) ]

The resin composition of the present embodiment may further contain an epoxy compound (G) other than the above-described epoxy resin (C) containing a bisphenol a structural unit and a hydrocarbon structural unit. The epoxy compound (G) is not particularly limited as long as it is a compound having 2 or more epoxy groups in 1 molecule other than the epoxy resin (C), and examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, 3-functional phenol type epoxy resin, 4-functional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, isocyanurate ring-containing epoxy resin, phenol aralkyl type epoxy resin, and the like, Or a halide of these. When the allyl group-containing compound (B) has an epoxy group, the epoxy compound (G) is a compound other than the allyl group-containing compound (B) having an epoxy group.

The content of the epoxy compound (G) is preferably 2.5 to 30 parts by mass, more preferably 5.0 to 27.5 parts by mass, and still more preferably 7.5 to 25 parts by mass, per 100 parts by mass of the resin solid content. When the content of the epoxy compound (G) is in the above range, flexibility, copper foil peel strength, chemical resistance, and desmear resistance of the obtained cured product tend to be further improved.

[ filling Material (H) ])

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

Among them, at least 1 selected from the group consisting of silica, alumina, magnesia, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride as an inorganic filler is preferably contained, and at least 1 selected from the group consisting of silica, alumina, and boehmite is more preferably contained. By using such a filler (H), the rigidity and warpage of the obtained cured product tend to be further improved.

The content of the filler (H) (particularly, an inorganic filler) is preferably 100 to 700 parts by mass, more preferably 100 to 450 parts by mass, and still more preferably 120 to 250 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the filler (H) is in the above range, the rigidity and warpage of the obtained cured product tend to be further improved.

[ silane coupling agent and wetting dispersant ]

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

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

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

[ other resins, etc. ]

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

[ other allyl-containing compounds ]

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

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

[ phenol resin ]

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

The content of the phenolic resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, per 100 parts by mass of the resin solid content. When the content of the phenol resin is in the above range, the obtained cured product tends to have further excellent adhesiveness, flexibility, and the like.

[ Oxetane resin ]

As the oxetane resin, a generally known one can be used, and the kind thereof is not particularly limited. Specific examples thereof include an alkyloxetane such as oxetane, 2-methyloxetane, 2-dimethyloxetane, 3-methyloxetane or 3, 3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3' -bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toyo Seiya Synthesis), OXT-121 (trade name manufactured by Toyo Seiya Synthesis), and the like. These oxetane resins can be used in 1 kind or in combination of 2 or more kinds. By containing such an oxetane resin, the resultant cured product tends to have more excellent adhesiveness, flexibility, and the like.

The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, per 100 parts by mass of the resin solid content. When the content of the oxetane resin is in the above range, the obtained cured product tends to have further excellent adhesion, flexibility, and the like.

[ benzoxazine compound ]

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

The content of the benzoxazine compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the benzoxazine compound is in the above range, the heat resistance and the like of the obtained cured product tend to be further excellent.

[ Compound having polymerizable unsaturated group ]

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

The content of the compound having a polymerizable unsaturated group is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the compound having a polymerizable unsaturated group is in the above range, the resultant cured product tends to have further excellent heat resistance, toughness, and the like.

[ curing accelerators ]

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

[ solvent ]

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

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

[ method for producing resin composition ]

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

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

[ use ]

The prepreg of the present embodiment satisfying the numerical ranges of the physical property parameters relating to the mechanical properties shown in formulae (1) to (5), preferably formulae (1A) to (5A), can be suitably used as an insulating layer, a laminate, a metal foil-clad laminate, a printed wiring board, or a multilayer printed wiring board. The laminate, the metal foil-clad laminate, and the printed wiring board (including a multilayer printed wiring board) will be described below.

[ laminate and Metal foil-clad laminate ]

The laminate sheet of the present embodiment has at least 1 or more sheets of the prepreg of the present embodiment laminated thereon. The metal foil-clad laminate of the present embodiment includes the laminate of the present embodiment (i.e., at least 1 or more of the prepregs of the present embodiment stacked) and metal foils (conductor layers) disposed on one or both surfaces of the laminate. By using a prepreg satisfying the numerical ranges of the physical property parameters relating to the mechanical properties (storage modulus and loss modulus) represented by the above-described formulae (1) to (5), preferably formulae (1A) to (5A), the laminate and the metal foil-clad laminate of the present embodiment have no clear glass transition temperature (no Tg) and have a tendency to be sufficiently reduced in warpage (to achieve low warpage).

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

The laminate, the method for forming the metal-clad laminate, and the conditions for forming the laminate are not particularly limited, and the methods and conditions for the usual laminate for printed wiring board and multilayer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used for molding the laminate sheet or the metal-clad laminate sheet. In addition, in the formation of the laminated plate or the metal-clad laminated plate (lamination formation), the temperature is usually 100 to 300 ℃ and the pressure is usually 2 to 100kgf/cm²And the heating time is within the range of 0.05-5 hours. Further, if necessary, the reaction may be carried out at a temperature of 150 to 300 ℃And (5) post-curing. Particularly, when a multistage press is used, the temperature is preferably 200 to 250 ℃ and the pressure is preferably 10 to 40kgf/cm from the viewpoint of sufficiently promoting curing of the prepreg²The heating time is 80 to 130 minutes, more preferably 215 to 235 ℃, and the pressure is 25 to 35kgf/cm²And the heating time is 90 to 120 minutes. Further, a multilayer board can also be produced by laminating and molding the prepreg and a separately prepared wiring board for an inner layer.

[ printed circuit board ]

The printed wiring board of the present embodiment is a printed wiring board having an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer includes the prepreg. For example, the metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern thereon. As described above, the metal foil-clad laminate of the present embodiment is not likely to have a clear glass transition temperature (no Tg) and is likely to be sufficiently reduced in warpage (low warpage is achieved), and therefore can be effectively used as a printed wiring board which requires such performance.

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

In this case, for example, the prepreg (the base material and the resin composition impregnated therein) constitutes an insulating layer.

In addition, in the case where a metal foil-clad laminate is not used, a conductor layer serving as a circuit may be formed on the prepreg to produce a printed wiring board. In this case, the conductor layer may be formed by electroless plating.

Further, as shown in fig. 9, the printed wiring board of the present embodiment is suitably: having a plurality of insulating layers and a plurality of conductor layers, the plurality of insulating layers comprising: a 1 st insulating layer (1) formed of at least 1 or more stacked prepregs, and a 2 nd insulating layer (2) formed of at least 1 or more stacked prepregs in a single-side direction (a lower direction in the drawing) of the 1 st insulating layer (1), the plurality of conductor layers including: a 1 st conductor layer (3) disposed between each of the plurality of insulating layers (1, 2), and a 2 nd conductor layer (3) disposed on the outermost layer of the plurality of insulating layers (1, 2). According to the findings of the present inventors and the like, it was confirmed that: while a typical laminate forms a multilayer printed circuit board by laminating another prepreg in the direction of both surfaces of a prepreg as one core substrate, for example, the prepreg of the present embodiment is particularly effective for a coreless multilayer printed circuit board (multilayer coreless substrate) produced by laminating another prepreg in which a 2 nd insulating layer (2) is formed only in the direction of one surface of one prepreg in which a 1 st insulating layer (1) is formed.

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

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

layer

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

As described above, the prepreg of the present embodiment having the above-described configuration, particularly the multilayer coreless substrate, does not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) as to satisfy the numerical range of physical property parameters relating to mechanical properties (storage modulus and loss modulus) represented by the above-described formulas (1) to (5) and preferably the formulas (1A) to (5A), and therefore can be effectively used particularly as a printed circuit board for semiconductor packaging and a multilayer coreless substrate.

Examples

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, 0.47 mol (in terms of OH group) of an α -naphthol aralkyl resin (SN495V, OH group equivalent: 236g/eq., manufactured by Nippon iron chemical Co., Ltd.; the number n of repeating units containing a naphthol aralkyl group is 1 to 5.) was dissolved in 500ml of chloroform, and 0.7 mol of triethylamine was added to the solution. While the temperature was maintained at-10 ℃ 300g of a chloroform solution of 0.93 mol of cyanogen chloride was added dropwise to the reactor over 1.5 hours, and after completion of the addition, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30g of chloroform was added dropwise to the reactor, and the reaction was terminated by stirring for 30 minutes. After the by-produced hydrochloride of triethylamine was filtered from the reaction solution, the obtained filtrate was washed with 500ml of 0.1N hydrochloric acid, and then washing was repeated 4 times with 500ml of water. Drying with sodium sulfate, evaporating at 75 deg.C, and further heating to 90 deg.CThen, degassing is carried out under reduced pressure to obtain a brown solid of the α -naphthol aralkyl type cyanate ester compound represented by the above formula (15) (R in the formula)⁶All are hydrogen atoms. ). The obtained alpha-naphthol aralkyl type cyanate ester compound was analyzed by infrared absorption spectroscopy, and the result was 2264cm^-1Absorption of cyanate ester groups was observed in the vicinity.

[ example 1]

45 parts by mass of a maleimide compound (A) (BMI-2300, manufactured by Daihu chemical Co., Ltd., maleimide equivalent 186G/eq.) 34 parts by mass of an alkenyl-substituted nadimide compound (E) (BANI-M, manufactured by Maruzen petrochemical Co., Ltd., allyl equivalent 286G/eq.) in an allyl-containing compound (B), 10 parts by mass of an epoxy resin (C) (ICEPLONEXA-4850) containing a bisphenol A-type structural unit and a hydrocarbon-based structural unit, manufactured by DIC Co., Ltd., epoxy equivalent 450G/eq.)10 parts by mass of an alpha-naphthol aralkyl type cyanate ester compound (SN495VCN, cyanate equivalent 261G/eq.)1 part by mass of synthetic example 1 as the cyanate ester compound (F), an epoxy compound (G) (NC-3000, FH chemical Co., Ltd., FH, and P.D., Epoxy equivalent: 320g/eq.)10 parts by mass, 120 parts by mass of slurry silica (SC-2050MB, manufactured by Admatech Company Limited) as a filler (H), 20 parts by mass of a silicone composite powder (KMP-600, manufactured by shin-Etsu chemical Co., Ltd.) as a filler (H), 5 parts by mass of a silane coupling agent (Z-6040, manufactured by Dow Corning Toray Co., Ltd.), 1 part by mass of a wetting dispersant (DISPERBYK-161, manufactured by BYK Japan KK), 0.5 part by mass of triphenylimidazole (manufactured by Wako pure chemical industries, Ltd.) as a curing accelerator, and 0.1 part by mass of zinc octoate (manufactured by Japan chemical industries Co., Ltd.) as a curing accelerator were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was impregnated into an E glass woven fabric (IPC #2116, manufactured by Kouzhi Co., Ltd.) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg having a resin composition content of 57 vol%.

[ example 2]

The varnish obtained in example 1 was applied to an E glass woven fabric (manufactured by Unitika ltd., IPC #1030) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.

[ example 3 ]

43 parts by mass of a maleimide compound (A) (BMI-2300), 32 parts by mass of an alkenyl-substituted nadimide compound (E) (BANI-M) in an allyl-containing compound (B), 10 parts by mass of an epoxy resin (C) (EPICLONEXA-4816, available from DIC corporation, epoxy equivalent: 403G/eq.) containing a bisphenol A-type structural unit and a hydrocarbon-based structural unit, 5 parts by mass of an α -naphthol aralkyl type cyanate ester compound (SN495VCN) of Synthesis example 1 as the cyanate ester compound (F), 10 parts by mass of an epoxy compound (G) (NC-3000FH, available from Nippon chemical Co., Ltd., epoxy equivalent: 320G/eq.) 100 parts by mass of a slurry silica (SC-2050MB) as a filler (H), a slurry silica (SC-5050MOB) as the filler (H), and a slurry silica (SC-5050MOB) as the filler (H), Admatechs Company Limited) 100 parts by mass, 20 parts by mass of a silicone composite powder (KMP-600) as a filler (H), 5 parts by mass of a silane coupling agent (Z-6040), 2 parts by mass of a wetting dispersant (DISPERBYK-111, BYK Japan KK) and 1 part by mass of a wetting dispersant (DISPERBYK-161), and 0.5 part by mass of triphenylimidazole as a curing accelerator and 0.1 part by mass of zinc octylate as a curing accelerator were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was impregnated into an E glass woven fabric (IPC #2116) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 57 vol%.

[ example 4 ]

The varnish obtained in example 3 was impregnated into an E glass woven fabric (IPC #1030) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 73 vol%.

[ comparative example 1]

51 parts by mass of a maleimide compound (A) (BMI-2300), 38 parts by mass of an alkenyl-substituted nadimide compound (E) (BANI-M) in an allyl-containing compound (B), 1 part by mass of an α -naphthol aralkyl type cyanate ester compound (SN495VCN) in Synthesis example 1 as a cyanate ester compound (F), 10 parts by mass of an epoxy compound (G) (NC-3000FH), 120 parts by mass of slurry silica (SC-2050MB) as a filler (H), 20 parts by mass of a silicone composite powder (KMP-600) as a filler (H), 5 parts by mass of a silane coupling agent (Z-6040), 1 part by mass of a wetting dispersant (DISPERBYK-161), 0.5 part by mass of triphenylimidazole as a curing accelerator, and 0.1 part by mass of zinc octylate as a curing accelerator were mixed, the varnish was obtained by diluting with methyl ethyl ketone. The varnish was impregnated into an E glass woven fabric (IPC #2116) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 57 vol%.

[ comparative example 2]

The varnish obtained in comparative example 1 was impregnated into an E glass woven fabric (IPC #1030) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 73 vol%.

[ comparative example 3 ]

49 parts by mass of a maleimide compound (A) (BMI-2300), 36 parts by mass of an alkenyl-substituted nadimide compound (E) (BANI-M) in an allyl-containing compound (B), 5 parts by mass of an α -naphthol aralkyl type cyanate ester compound (SN495VCN) in Synthesis example 1 as the cyanate ester compound (F), 10 parts by mass of an epoxy compound (G) (NC-3000FH), 100 parts by mass of slurry silica (SC-2050MB) as a filler (H), 100 parts by mass of slurry silica (SC-5050MOB) as the filler (H), 20 parts by mass of an organosilicon composite powder (KMP-600) as the filler (H), 5 parts by mass of a silane coupling agent (Z-6040), 2 parts by mass of a wet dispersant (DISPERBYK-111) and 1 part by mass of a wet dispersant (DISPERBYK-161), And 0.5 part by mass of triphenylimidazole as a curing accelerator and 0.1 part by mass of zinc octoate as a curing accelerator were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was impregnated into an E glass woven fabric (IPC #2116) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 57 vol%.

[ comparative example 4 ]

The varnish obtained in comparative example 3 was impregnated into an E glass woven fabric (IPC #1030) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.

[ comparative example 5 ]

15 parts by mass of a maleimide compound (BMI-70, manufactured by Dahe Kabushiki Kaisha, maleimide equivalent: 221G/eq.) 50 parts by mass of an α -naphthol aralkyl type cyanate ester compound (SN495VCN) of Synthesis example 1 as the cyanate ester compound (F), 50 parts by mass of an epoxy compound (G) (NC-3000FH), 100 parts by mass of slurry silica (SC-2050MB) as the filler (H), 100 parts by mass of slurry silica (SC-5050MOB) as the filler (H), and 20 parts by mass of silicone composite powder (KMP-600) as the filler (H), 5 parts by mass of a silane coupling agent (Z-6040), 2 parts by mass of a wet dispersant (DISPERBYK-111) and 1 part by mass of a wet dispersant (DISPERBYK-161), and 0.5 parts by mass of triphenylimidazole as a curing accelerator and 0.1 part by mass of zinc octoate as a curing accelerator were mixed, the varnish was obtained by diluting with methyl ethyl ketone. The varnish was impregnated into an E glass woven fabric (IPC #2116) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing a resin composition in an amount of 57 vol%.

[ comparative example 6 ]

The varnish obtained in comparative example 5 was impregnated into an E glass woven fabric (IPC #1030) and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.

[ evaluation of physical Properties measurement ]

Using the prepregs obtained in examples 1 to 4 and comparative examples 1 to 6, samples for measurement and evaluation of physical properties were prepared by the procedures shown in the following items, and measurement and evaluation were performed on mechanical properties (storage modulus and loss modulus), physical properties parameters related to the mechanical properties in expressions (1) to (5) and expressions (1A) to (5A), glass transition temperature (Tg), warpage amount (2 types), and substrate shrinkage before and after reflow step. The results of the examples are shown together in table 1, and the results of the comparative examples are shown together in table 2.

[ mechanical characteristics ]

Copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 6, and the pressure was 30kgf/cm²And laminated molding (thermosetting) at 230 ℃ for 100 minutes to obtainA copper clad laminate having a predetermined insulating layer thickness. The obtained copper clad laminate was cut into a size of 5.0mm × 20mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using the measurement sample, mechanical properties (storage modulus E' and loss modulus E ") were measured by a DMA method according to JIS C6481 using a dynamic viscoelasticity analyzer (TA Instruments) (average value of n ═ 3)

[ glass transition temperature (Tg) ]

Copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 6, and the pressure was 30kgf/cm²Then, the laminate was laminated and molded (heat-cured) at 230 ℃ for 100 minutes to obtain a copper clad laminate having a predetermined insulating layer thickness. The obtained copper clad laminate was cut into a size of 12.7mm × 2.5mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using the measurement sample, the glass transition temperature (Tg) was measured by a DMA method according to JIS C6481 using a dynamic viscoelasticity analyzer (TA Instruments) (n is an average value of 3).

[ amount of warp: bimetallic strip method)

First, copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 6, and the pressure was 30kgf/cm²Then, the laminate was laminated and formed (heat-cured) at 220 ℃ for 120 minutes to obtain a copper clad laminate. Next, the copper foil is removed from the obtained copper clad laminate. Next, 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 6 was further placed on one surface of the laminate from which the copper foil was removed, and the copper foil (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) was placed on both upper and lower surfaces thereof, and the resultant laminate was pressed at a pressure of 30kgf/cm²Then, the laminate was laminated and formed (heat-cured) at 220 ℃ for 120 minutes to obtain a copper clad laminate again. Further, the copper foil is removed from the obtained copper clad laminate to obtain a laminate. Then, a 20mm × 200mm strip-shaped sheet was cut out from the resulting laminated sheet, and the surface of the prepreg laminated on the 2 nd sheet was set as the upper side, and a metal was usedThe maximum value of the warpage amount at both ends in the longitudinal direction was measured with a ruler, and the average value thereof was defined as the "warpage amount" by the bimetal method.

[ amount of warp: multilayer coreless substrate ]

First, as shown in FIG. 1, a carrier copper foil surface of an extra thin copper foil (b1) (MT18Ex, manufactured by Mitsui Metal mining Co., Ltd., thickness 5 μm) with a carrier was disposed on both surfaces of a prepreg as a support (a), prepregs (c1) obtained in examples 1 to 4 and comparative examples 1 to 6 were further disposed thereon, and a copper foil (d) (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) was further disposed thereon, and the pressure was 30kgf/cm²Then, the laminate was laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate shown in FIG. 2.

Next, the copper foil (d) of the obtained copper clad laminate shown in fig. 2 is etched in a predetermined wiring pattern as shown in fig. 3, for example, to form a conductor layer (d'). Next, the prepregs (c2) obtained in examples 1 to 4 and comparative examples 1 to 6 were placed on the laminate sheet shown in FIG. 3 having the conductor layer (d') formed thereon as shown in FIG. 4, and the extra thin copper foil (b2) (MT18Ex, manufactured by Mitsui Metal mining Co., Ltd., thickness 5 μm) with a carrier was further placed thereon at a pressure of 30kgf/cm²Then, the laminate was laminated at 230 ℃ for 120 minutes to obtain a copper clad laminate shown in FIG. 5.

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

[ yield of substrate before and after reflow soldering Process ]

Copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 6, and the pressure was 30kgf/cm²And laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate. Next, the obtained copper clad laminate was drilled at 9 points uniformly in a grid pattern with a drill, and then the copper foil was removed.

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

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

[ Table 1]

[ Table 2]

Industrial applicability

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

Claims

1. A prepreg, comprising: a thermosetting resin, a filler and a base material,

E’(200℃)/E’(30℃)≤0.90…(1)

E’(260℃)/E’(30℃)≤0.85…(2)

E’(330℃)/E’(30℃)≤0.80…(3)

E”max/E’(30℃)≤3.0％…(4)

E”min/E’(30℃)≥0.5％…(5)

in each formula, E ' represents the storage modulus of the cured product at the temperature shown in the brackets, E ' max represents the maximum value of the loss modulus of the cured product in the temperature range of 30-330 ℃, and E ' min represents the minimum value of the loss modulus of the cured product in the temperature range of 30-330 ℃.

2. The prepreg according to claim 1, which further satisfies mechanical properties represented by the following formula (6A),

E’(30℃)≤30GPa…(6A)

wherein E' represents the storage modulus of the cured product at the temperature shown in parentheses.

3. A prepreg according to claim 1 or 2, wherein the substrate is a glass substrate.

4. The prepreg according to claim 3, wherein the glass substrate is composed of fibers of 1 or more kinds of glass selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.

5. A laminate having at least 1 or more prepregs as claimed in any one of claims 1 to 4 laminated thereon.

6. A metal-clad laminate comprising:

at least 1 or more stacked prepregs according to any of claims 1 to 4, and

and a metal foil disposed on one or both surfaces of the prepreg.

7. A printed circuit board, having:

an insulating layer formed from the prepreg according to any one of claims 1 to 4, and

and a conductor layer formed on the surface of the insulating layer.

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

the plurality of insulating layers includes: a 1 st insulating layer formed from at least 1 or more sheets of the prepreg according to any one of claims 1 to 4 stacked, and a 2 nd insulating layer formed from at least 1 or more sheets of the prepreg according to any one of claims 1 to 4 stacked in a single-side direction of the 1 st insulating layer,