JP6681052B2 - Prepreg, laminated board, metal foil clad laminated board, printed wiring board, and multilayer printed wiring board - Google Patents

Description

  The present invention relates to a prepreg, 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 that are widely used in electronic devices, communication devices, personal computers, etc. have become more sophisticated and miniaturized, high integration and high-density mounting of each component for semiconductor packages have been accelerated in recent years. ing. Along with this, various characteristics required for printed wiring boards for semiconductor packages are becoming more and more severe. The 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, etc. Can be mentioned. In addition to these, controlling warpage (achieving low warpage) of printed wiring boards, especially multilayer coreless boards, has recently become an important issue, and various measures have been taken. There is.

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

  As a method of suppressing the warpage of the semiconductor plastic package, in addition to lowering the thermal expansion of the printed wiring board, increasing the rigidity of the laminated board (increasing the rigidity) and increasing the glass transition temperature of the laminated board (high Tg Has been studied (see, for example, Patent Documents 4 and 5).

JP, 2013-216884, A Japanese Patent No. 3173332 JP, 2009-035728, A JP, 2013-001807, A JP, 2011-178992, A

  However, according to a detailed study by the present inventors, even with the above-described conventional technique, it is still impossible to sufficiently reduce the warpage of the printed wiring board, particularly the multilayer coreless substrate, and further improvement is desired. It is rare.

  That is, the present invention does not have a clear glass transition temperature (Tg) (so-called Tg-less) and can sufficiently reduce the warp (achieve a low warp) of a printed wiring board, particularly a multilayer coreless substrate. An object of the present invention is to provide a prepreg, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring board that can be manufactured.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have hitherto been concerned with the warp behavior of printed wiring boards for semiconductor plastic packages, in the cured product of the prepreg, having a larger storage elastic modulus at heat, Also, although it has been considered that a resin composition capable of achieving a higher elastic modulus maintenance rate is effective, it has been found that this is not always the case. Further, the present inventors, as a result of intensive research, in the physical property parameters related to specific mechanical properties in the cured product obtained by thermosetting the prepreg, by the numerical value of the physical property parameter satisfies a predetermined condition range, It has been found that the above problems can be solved. That is, the inventors have found that the above problems can be solved by satisfying a specific condition range in the storage elastic modulus at heat and loss elastic modulus in a cured product obtained by thermosetting a prepreg, and completed the present invention.

That is, the present invention is as follows.
[1]
A thermosetting resin,
A filler,
Base material,
A prepreg containing
A cured product obtained by heat curing the prepreg at 230 ° C. for 100 minutes has the following formulas (1) to (5);
E ′ (200 ° C.) / E ′ (30 ° C.) ≦ 0.90 (1)
E ′ (260 ° C.) / E ′ (30 ° C.) ≦ 0.85 (2)
E ′ (330 ° C.) / E ′ (30 ° C.) ≦ 0.80 (3)
E ″ max / E ′ (30 ° C.) ≦ 3.0% (4)
E ″ min / E ′ (30 ° C.) ≧ 0.5% (5)
(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. And 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.)
Satisfies the numerical range of physical property parameters related to mechanical properties,
Prepreg.

[2]
Formula (6A) below;
E ′ (30 ° C.) ≦ 30 GPa (6A)
(In the formula, E ′ represents the storage elastic modulus of the cured product at the temperature shown in parentheses.)
Further satisfy the mechanical characteristics represented by,
The prepreg according to [1].

[3]
The substrate is a glass substrate,
The prepreg according to [1] or [2].

[4]
The glass substrate is composed of fibers of at least one glass selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. is there,
Prepreg described in [3]

[5]
At least one or more laminated prepregs according to any one of [1] to [4],
Laminated board.

[6]
At least one or more laminated prepreg according to any one of [1] to [4],
A metal foil arranged on one side or both sides of the prepreg,
A metal foil-clad laminate.

[7]
An insulating layer formed of the prepreg according to any one of [1] to [4],
A conductor layer formed on the surface of the insulating layer,
Printed wiring board having.

[8]
A first insulating layer formed of the prepreg according to any one of [1] to [4], wherein at least one sheet is laminated, and at least one sheet is laminated in one surface direction of the first insulating layer. A plurality of insulating layers formed of the second insulating layer formed of the prepreg according to any one of [1] to [4],
A plurality of conductor layers including a first conductor layer arranged between each of the plurality of insulating layers, and a second conductor layer arranged on the surface of the outermost layer of the plurality of insulating layers;
Multilayer printed wiring board having.

  According to the present invention, a printed wiring board, especially a prepreg, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring, which can sufficiently reduce the warpage (achieve a low warpage) of a multilayer coreless substrate, are provided. A 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 showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a process flow figure showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a process flow figure showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a process flow figure showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a process flow figure showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a process flow figure showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a process flow figure showing an example of the procedure of producing the panel of a multilayer coreless substrate. It is a fragmentary sectional view showing an example of composition of a panel of a multilayer coreless substrate.

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

[Prepreg]
The prepreg of the present embodiment contains a base material and a resin composition described below which is impregnated or applied to the base material. The method for producing the prepreg can be performed according to a conventional method and is not particularly limited. For example, after the substrate is impregnated with or coated with the resin composition in the present embodiment, it 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.

  In addition, in the prepreg of the present embodiment, a cured product obtained by heat curing the prepreg under conditions of 230 ° C. and 100 minutes has a numerical range of physical property parameters regarding mechanical properties represented by the following formulas (1) to (5). And preferably satisfies the numerical range of the physical property parameters relating to mechanical properties represented by the following formulas (1A) to (5A).

E ′ (200 ° C.) / E ′ (30 ° C.) ≦ 0.90 (1)
E ′ (260 ° C.) / E ′ (30 ° C.) ≦ 0.85 (2)
E ′ (330 ° C.) / E ′ (30 ° C.) ≦ 0.80 (3)
E ″ max / E ′ (30 ° C.) ≦ 3.0% (4)
E ″ min / E ′ (30 ° C.) ≧ 0.5% (5)
0.40 ≦ E ′ (200 ° C.) / E ′ (30 ° C.) ≦ 0.90 (1A)
0.40 ≦ E ′ (260 ° C.) / E ′ (30 ° C.) ≦ 0.85 (2A)
0.40 ≦ E ′ (330 ° C.) / E ′ (30 ° C.) ≦ 0.80 (3A)
0.5% ≦ E ″ max / E ′ (30 ° C.) ≦ 3.0% (4A)
3.0% ≧ E ″ min / E ′ (30 ° C.) ≧ 0.5% (5A)

  Here, 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 loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. And 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. (E ″ represents the loss elastic modulus of the cured product).

  Conventionally, with respect to the warp behavior of a printed wiring board, it has been considered that a cured resin of a prepreg is a resin composition capable of achieving a higher storage elastic modulus under heat and a higher elastic modulus maintenance ratio. This is not always the case, and 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. for 100 minutes are the above formulas (1) to (5), preferably the formula (1A) to By being in the range of (5A), the glass transition temperature (Tg) can be sufficiently increased, and the warpage amount of the laminate, the metal foil-clad laminate, the printed wiring board, especially the multilayer coreless substrate itself is sufficient. Can be reduced to.

  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. for 100 minutes are expressed by the above formulas (1) to (5), preferably formulas (1A) to (5A). Within the range, the glass transition temperature does not exist clearly (Tg-less), and the warp of the printed wiring board (particularly, the multilayer coreless substrate) is sufficiently reduced (low warp is achieved). It becomes possible. That is, satisfying the formulas (4) and (5), preferably the formulas (4A) and (5A) relating to the loss elastic modulus, is synonymous with the absence of a clear glass transition temperature (Tg) (less Tg). However, the cured product satisfies only the formulas (4) and (5), preferably the formulas (4A) and (5A), and does not satisfy the formulas (1) to (3), preferably the formulas (1A) to (3A). Although the loss elastic modulus itself is small and difficult to extend, when the printed wiring board is made, the difficulty of extension causes damage and it is difficult to achieve low warpage. On the other hand, the cured product satisfies not only Formulas (4) and (5), preferably Formulas (4A) and (5A), but also Formulas (1) to (5), preferably Formulas (1A) to (5A). Those having less Tg tend not to be easily stretched, and a low warp of the printed wiring board tends to be easily achieved.

  Furthermore, the prepreg of the present embodiment preferably satisfies the mechanical properties represented by the following formula (6A), and more preferably satisfies the mechanical properties represented by the following formula (6) and / or formula (6B). is there.

E ′ (30 ° C.) ≦ 30 GPa (6A)
E ′ (30 ° C.) ≦ 25 GPa (6)
1 GPa ≦ E ′ (30 ° C.) (6B)
Here, in the formula, E ′ represents the storage elastic modulus of the cured product at the temperature shown in parentheses. That is, the E '(30 ° C.) of the prepreg of this embodiment is preferably 30 GPa or less, and more preferably 25 GPa or less. The lower limit of E ′ (30 ° C.) is not particularly limited, but is preferably 1 GPa or more.

  When the mechanical properties of the cured product obtained by heat curing the prepreg at 230 ° C. for 100 minutes are within the range of the above formula (6), it is possible to further reduce the warpage of the multilayer coreless substrate. Become.

The method for measuring the mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ″) of the cured product of the prepreg is not particularly limited and can be measured, 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 laminated molding (thermosetting for 100 minutes at a pressure of 30 kgf / cm ² and 230 ° C.) ) Is performed to obtain a copper foil-clad laminate having a predetermined insulating layer thickness. Then, the obtained copper foil-clad laminate is cut into a size of 5.0 mm × 20 mm with a dicing saw, and then the surface copper foil 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 using a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481. be able to. At this time, an average value of n = 3 may be obtained.

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

  The base material is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used according to the intended use and performance. Examples of the base material include a glass base material, an inorganic base material other than glass, an organic base material, and the like. Among these, a glass base material is particularly preferable from the viewpoint of high rigidity and heating dimensional stability. . Specific examples of fibers constituting these base materials are not particularly limited, and examples of glass base materials include 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 Examples of the inorganic base material other than glass include inorganic fibers other than glass such as quartz. Further, as the organic base material, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene-3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno-Products Co., Ltd.) Polyamide such as 2,6-hydroxynaphthoic acid / para-hydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Seiren); Polypara; Examples of organic fibers include phenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. These base materials may be used alone or in combination of two or more.

The shape of the base material is not particularly limited, and examples thereof include woven cloth, non-woven cloth, roving, chopped strand mat, surfacing mat, and the like. The weaving method of the woven fabric is not particularly limited, but, for example, plain weave, satin weave, twill weave, etc. are known, and can be appropriately selected from these known ones depending on the intended use and performance. . Further, those obtained by subjecting these to a fiber-opening treatment or a glass woven fabric surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but normally, 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 preferable.

[Resin composition]
The resin composition of the present embodiment used for the prepreg is not particularly limited as long as it contains a thermosetting resin and a filler, and includes, for example, a maleimide compound (A) and an allyl group-containing compound (B). , An epoxy resin (C) comprising a bisphenol A type structural unit and a hydrocarbon type structural unit, and relates to mechanical properties represented by the above formulas (1) to (5), preferably formulas (1A) to (5A). A composition that can realize the numerical range of the physical property parameter can be appropriately selected. Using a prepreg containing such a resin composition and a base material, a laminated board, a metal foil-clad laminated board, a printed wiring board, particularly a multilayer coreless board, can tend to sufficiently reduce the amount of warpage due to heating such as reflow. It is in.

[Maleimide compound (A)]
The maleimide compound (A) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule, and examples thereof include 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 (7), 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 (7) is preferable, and maleimide compounds represented by the following formula (7) are particularly preferable. By including such a maleimide compound (A), the thermal expansion coefficient of the obtained cured product is further reduced, and the heat resistance and the glass transition temperature (Tg) tend to be further improved.

Here, in the formula (7), each R ₅ independently represents a hydrogen atom or a methyl group, and preferably a hydrogen atom. In the formula (7), n ₁ represents 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, and still more preferably 25 to 50 parts by mass with respect to 100 parts by mass of the resin solid content. , Particularly preferably 35 to 50 parts by mass, and even more preferably 35 to 45 parts by mass. When the content of the maleimide compound (A) is within the above range, the coefficient of thermal expansion of the obtained cured product tends to be lower, 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 is a compound having one or more allyl groups in the molecule, but may further have a reactive functional group other than the allyl group. The reactive functional group other than the allyl group is not particularly limited, and examples thereof include a cyanate group (cyanate ester group), a hydroxyl group, an epoxy group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric acid group. Among these, at least one selected from the group consisting of a cyanate group (cyanate ester group), a hydroxyl group, and an epoxy group is preferable, and a cyanate group (cyanate ester group) is more preferable. By having a hydroxyl group, a cyanate group (cyanate ester group), and an epoxy group, it has high bending strength and bending elastic modulus, low dielectric constant, high glass transition temperature (high Tg), low thermal expansion coefficient, and thermal The conductivity tends to be improved.

  As the allyl group-containing compound (B), one type may be used alone, or two or more types may be used in combination. When two or more kinds of allyl group-containing compound (B) having a reactive functional group other than an allyl group are used in combination, the reactive functional groups other than the allyl group may be the same or different. Among them, it is preferable that the allyl group-containing compound (B) contains an allyl group-containing compound in which the reactive functional group is a cyanate group and an allyl group-containing compound in which the reactive functional group is an epoxy group. By using such an allyl group-containing compound (B) together, the bending strength, the bending elastic modulus, the glass transition temperature (Tg), and the thermal conductivity tend to be further improved.

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

  Further, it is particularly preferable to use an allylphenol derivative (D) and / or an alkenyl-substituted nadimide compound (E) described later as the allyl group-containing compound (B). By using such an allyl group-containing compound (B), the glass transition temperature (Tg), thermal expansion coefficient, and 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, and still more preferably 20 to 75 parts by mass with respect to 100 parts by mass of the resin solid content. Parts, and particularly preferably 25 to 40 parts by mass. When the content of the allyl group-containing compound (B) is within the above range, the obtained cured product has flexibility, bending strength, bending elastic modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and Copper foil peel strength tends to be further improved.

(Allylphenol derivative (D))
The allylphenol 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, for example, bisphenol in which a hydrogen atom of the aromatic ring is substituted with an allyl group. , The hydrogen atom of the aromatic ring is substituted with an allyl group, the phenolic hydroxyl group, in the reactive functional group other than the above-mentioned allyl group, modified bisphenol compounds modified with a reactive functional group other than the hydroxyl group, and the like, Specific examples include compounds represented by the following formula (8), and more specific examples include diallyl bisphenol A, cyanate ester compounds of diallyl bisphenol A, and diallyl bisphenol A type epoxy.

  In formula (8), Ra's each independently represent a reactive substituent other than an allyl group.

  The compound represented by the formula (8) is not particularly limited, and examples thereof include a compound represented by the following formula (8a) and / or a compound represented by the following formula (8b). By using such an allylphenol derivative (D), bending strength, bending elastic 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, but includes, 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.

  The number of allyl groups in one molecule of the allylphenol derivative (D) is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2. When the number of allyl groups in one molecule of allylphenol derivative (D) is within the above range, bending strength, bending elastic modulus, copper foil peel strength, glass transition temperature (Tg) are further improved, and thermal expansion coefficient is increased. It is low and tends to have excellent thermal conductivity.

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

  The suitable range of the content of the allylphenol derivative (D) is based on the content of the above-mentioned allyl group-containing compound (B).

(Alkenyl-substituted nadimide compound (E))
The alkenyl-substituted nadimide compound (E) is not particularly limited as long as it is a compound having at least one alkenyl-substituted nadimide group in the molecule. Among these, the compound represented by the following formula (9) is preferable. By using such an alkenyl-substituted nadimide compound (E), the coefficient of thermal expansion of the obtained cured product tends to further decrease, and the heat resistance tends to further improve.

In formula (9), each R ₁ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, or naphthylene. A group or a group represented by the following formula (10) or (11) is shown.

In formula (10), R ₃ represents a methylene group, an isopropylidene group, or a substituent represented by CO, O, S, or SO ₂ .

Wherein (11), R ₄ are each independently an alkylene group, or a cycloalkylene group having a carbon number of 5-8 having from 1 to 4 carbon atoms.

  Further, the alkenyl-substituted nadimide 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 coefficient of thermal expansion of the obtained cured product tends to further decrease, and the heat resistance tends to further improve.

  As the alkenyl-substituted nadiimide compound (E), a commercially available product can be used. The commercially available product is not particularly limited, and examples thereof include BANI-M (manufactured by Maruzen Petrochemical Co., Ltd., compound represented by formula (12)), BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.), The compound represented by the formula (13)) and the like can be mentioned. These may be used alone or in combination of two or more.

  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 with respect to 100 parts by mass of the resin solid content. Further, even more preferably, the total content of the allylphenol derivative (D) and the alkenyl-substituted nadiimide compound (E) is preferably 20 to 50 parts by mass, and more preferably 100 parts by mass of the resin solid content. Is 35 to 45 parts by mass. When the content of the alkenyl-substituted nadiimide compound (E) is within the above range, the coefficient of thermal expansion of the obtained cured product tends to further decrease and the heat resistance tends to further improve.

[Epoxy resin (C) comprising bisphenol A type structural unit and hydrocarbon type structural unit]
The epoxy resin (C) composed of a bisphenol A type structural unit and a hydrocarbon type structural unit is a compound having at least one bisphenol A type structural unit and one or more hydrocarbon type structural unit in the molecule. There is no particular limitation. Among these, the compound represented by the following formula (14) is preferable. By using the epoxy resin (C) composed of such a bisphenol A type structural unit and a hydrocarbon type structural unit, the storage elastic modulus E ′ of the obtained cured product upon heating tends to be a value suitable for suppressing warpage. is there.

Here, in formula (14), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R _{3 to} R ₆ are each independently a hydrogen atom, a methyl group, or a chlorine atom. , Or a bromine atom, and X is an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group. Represents a group or an alkylene group having 2 to 15 carbon atoms, and n represents a natural number.

  A commercially available epoxy resin (C) composed of the bisphenol A type structural unit and the hydrocarbon type structural unit may be used. The commercially available product is not particularly limited, and examples thereof include EPICLON EXA-4850-150 (manufactured by DIC Corporation, compound having a structure represented by formula (14)), EPICLON EXA-4816 (DIC (stock). ), A compound in which X in the formula (14) is an ethylene group) and the like. These may be used alone or in combination of two or more.

  The content of the epoxy resin (C) composed of the bisphenol A type structural unit and the hydrocarbon type structural unit is preferably 5 to 25 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin solid content. Parts, and more preferably 10 to 20 parts by mass. When the content of the epoxy resin (C) composed of the bisphenol A type structural unit and the hydrocarbon type structural unit is within the above range, the obtained cured product has a storage elastic modulus E ′ suitable for suppressing warpage. Tends to be.

[Cyanate ester compound (F)]
The resin composition of this 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-mentioned allylphenol derivative (D). For example, a naphthol aralkyl type cyanate ester represented by the following formula (15), A novolac type cyanate ester represented by the formula (16), a biphenylaralkyl type cyanate ester, bis (3,5-dimethyl4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, and 1,3-disiocyanate. Anatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-disi Anatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6- Licyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2'-bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters and the like can be mentioned. These cyanate ester compounds (F) may be used alone or in combination of two or more.

In formula (15), each R ₆ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the formula (15), n ₂ represents an integer of 1 or more. The upper limit of n ₂ is usually 10 and preferably 6.

In formula (16), R _7's each independently represent a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the formula (16), n ₃ represents an integer of 1 or more. The upper limit of n ₃ is usually 10, and preferably 7.

  Among these, the cyanate ester compound (F) is composed of a naphthol aralkyl cyanate ester represented by the formula (15), a novolac cyanate ester represented by the formula (16), and a biphenylaralkyl 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 cyanate represented by the formula (15) and a novolac cyanate represented by the formula (16). More preferably. By using such a cyanate ester compound (F), a cured product having more excellent flame retardancy, higher curability and 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 method is not particularly limited, for example, a method of reacting a phenol resin and a cyanogen halide in an inert organic solvent in the presence of a basic compound, a salt of a phenol resin and a basic compound, water There is a method in which it is formed in a solution containing it, and then the obtained salt and cyanogen halide are subjected to a two-phase interfacial reaction.

  The phenol resin as a raw material of these cyanate ester compounds (F) is not particularly limited, but for example, a naphthol aralkyl type phenol resin, a novolac type phenol resin, or a biphenyl aralkyl type phenol resin represented by the following formula (17) is used. Can be mentioned.

In formula (17), each R ₈ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the formula (17), n ₄ represents an integer of 1 or more. The upper limit of n ₄ is usually 10, and preferably 6.

  The naphthol aralkyl type phenol resin represented by the formula (17) can be obtained by condensing the naphthol aralkyl resin and cyanic acid. The naphthol aralkyl-type phenol resin is not particularly limited, and examples thereof include naphthols such as α-naphthol and β-naphthol, p-xylylene glycol, α, α′-dimethoxy-p-xylene, and 1,4-. Examples thereof include those obtained by the reaction with benzenes such as di (2-hydroxy-2-propyl) benzene. The naphthol aralkyl type 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 (F) is preferably 0.5 to 45 parts by mass, more preferably 10 to 45 parts by mass, and further preferably 15 to 100 parts by mass of the resin solid content. It is 45 parts by mass, and more preferably 20 to 35 parts by mass. 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 (G)]
The resin composition of the present embodiment may further contain an epoxy compound (G) other than the epoxy resin (C) composed of the bisphenol A type structural unit and the hydrocarbon type structural unit described above. The epoxy compound (G) is not particularly limited as long as it is a compound other than the epoxy resin (C) and has two or more epoxy groups in one molecule, and examples thereof include bisphenol A type epoxy resin and 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 novolak type epoxy resin Resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, a polyol type epoxy resin, isocyanurate ring-containing epoxy resin, or these halides and the like. When the allyl group-containing compound (B) has an epoxy group, the epoxy compound (G) is 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 100 parts by mass of the resin solid content. It is 7.5 to 25 parts by mass. When the content of the epoxy compound (G) is within the above range, the flexibility, copper foil peel strength, chemical resistance, and desmear resistance of the obtained cured product tend to be further improved.

[Filler (H)]
The resin composition of this embodiment may further contain a filler (H). The filler (H) is not particularly limited, but examples thereof include an inorganic filler and an organic filler, and it is preferable to include an inorganic filler of both, and the organic filler is used together with the inorganic filler. That is preferable. 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; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride; metal sulphates such as barium sulfate; aluminum hydroxide, heat treated aluminum hydroxide (heating aluminum hydroxide) Treated with some water of crystallization), 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 ta Ku, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (E glass, T glass, D glass, Glass fine powders such as S glass and Q glass are included), hollow glass, spherical glass and the like. The organic filler is not particularly limited, and examples thereof include rubber powder such as styrene type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; silicone composite powder. To be The filler (H) may be used alone or in combination of two or more.

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

  The content of the filler (H) (particularly the inorganic filler) is preferably 100 to 700 parts by mass, more preferably 100 to 450 parts by mass, and still more preferably 100 parts by mass of the resin solid content. It is 120 to 250 parts by mass. When the content of the filler (H) is within the above range, the obtained cured product tends to have higher rigidity and lower warpage.

[Silane coupling agent and wetting dispersant]
The resin composition of this embodiment may further contain a silane coupling agent and a wetting and dispersing agent. By including the silane coupling agent and the wetting dispersant, the dispersibility of the filler (H), the resin component, the filler (H), and the adhesive strength of the base material described below tend to be further improved.

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

  The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. 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 of the present embodiment contains an allyl group-containing compound (hereinafter also referred to as “other allyl group-containing compound”), a phenol resin, an oxetane resin, other than the above-mentioned allyl group-containing compound (B), if necessary. You may further contain 1 type (s) or 2 or more types selected from the group which consists of a benzoxazine compound and the compound which has a polymerizable unsaturated group. The inclusion of such other resin or the like tends to further improve the copper foil peel strength, bending strength, bending elastic modulus, and the like of the obtained cured product.

[Other allyl group-containing compounds]
Other allyl group-containing compounds are not particularly limited, for example, 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, more preferably 10 to 45 parts by mass, and more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. And more preferably 20 to 35 parts by mass. When the content of the other allyl group-containing compound is within the above range, the resulting cured product tends to have improved flexural strength, flexural modulus, heat resistance and chemical resistance.

[Phenolic resin]
As the phenol resin, a generally known phenol resin can be used as long as it is a phenol resin having two or more hydroxy groups in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolak 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 novolac type phenol resin, phenol aralkyl type phenol resin , Naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol 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 may be used alone or in combination of two or more. By containing such a phenol resin, the cured product obtained tends to be superior in adhesiveness and flexibility.

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

[Oxetane resin]
As the oxetane resin, a generally known one can be used, and the type thereof is not particularly limited. Specific examples thereof include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, and 3,3 ′. -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toagosei Co., Ltd.), OXT-121 (product of Toagosei) Product name) and the like. These oxetane resins can be used alone or in combination of two or more. By containing such an oxetane resin, the cured product obtained tends to be superior in adhesiveness and flexibility.

  The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. 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, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name of Konishi Chemical Co., Ltd.) bisphenol F type benzoxazine BF-BXZ (trade name of Konishi Chemical Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (trade name of Konishi Chemical Co., Ltd.) Name) etc. These benzoxazine compounds can be used alone or in combination of two or more. By including such a benzoxazine compound, the obtained cured product tends to be 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 with respect to 100 parts by mass of the resin solid content. When the content of the benzoxazine compound is within the above range, the obtained 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 type thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di ( (Meth) of monohydric or polyhydric alcohols 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 unsaturated group-containing compounds may be used alone or in combination of two or more. By containing such a compound having a polymerizable unsaturated group, the resulting cured product tends to be superior in heat resistance and toughness.

  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 100 parts by mass of the resin solid content. 80 parts by mass. When the content of the compound having a polymerizable unsaturated group is within the above range, the obtained cured product tends to be more excellent in heat resistance and toughness.

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 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 Such as phenol; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone, etc .; these organometallic salts Dissolved in a hydroxyl group-containing compound such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; organic tin compounds such as dioctyl tin oxide and other alkyl tin and alkyl tin oxide. To be Among these, triphenylimidazole is particularly preferable because it accelerates the curing reaction and tends to have excellent glass transition temperature (Tg) and coefficient of thermal expansion.

〔solvent〕
The resin composition of this embodiment may further contain a solvent. By including the solvent, the viscosity at the time of preparation of the resin composition is lowered, the handling property is further improved, and the impregnating 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; aromatics such as toluene and xylene. Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate. The solvent may be used alone or in combination of two or more.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method in which each component is sequentially mixed in a solvent and sufficiently stirred. 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 (H) in the resin composition can be improved by performing the stirring and dispersion treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The stirring, mixing, and kneading treatments described above can be appropriately performed using, for example, a device intended for mixing such as a ball mill or a bead mill, or a known device such as a revolution or rotation type mixing device.

  Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used if necessary. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. The specific example is as described above.

[Use]
The prepreg satisfying the numerical ranges of the physical properties parameters relating to the mechanical properties represented by the formulas (1) to (5), preferably the formulas (1A) to (5A), of the present embodiment is an insulating layer, a laminate, or a metal foil-clad laminate. It can be suitably used as a printed wiring board, or a multilayer printed wiring board. Hereinafter, a laminated board, a metal foil-clad laminated board, and a printed wiring board (including a multilayer printed wiring board) will be described.

[Laminates and metal foil-clad laminates]
The laminated board of the present embodiment has at least one prepreg of the present embodiment laminated. Further, the metal foil-clad laminate of the present embodiment includes the laminate of the present embodiment (that is, at least one or more of the prepregs of the present embodiment), and the metal foil arranged on one side or both sides of the laminate. (Conductor layer). The use of a prepreg satisfying the numerical ranges of the physical parameters relating to the mechanical properties (storage modulus and loss modulus) represented by the above formulas (1) to (5), preferably formulas (1A) to (5A), The laminated sheet and the metal foil-clad laminated sheet of the embodiment do not have a clear glass transition temperature (Tg-less) and tend to sufficiently reduce warpage (achieve low warpage).

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

The method and conditions for forming the laminate or the metal foil-clad laminate are not particularly limited, and general techniques and conditions for the laminate for printed wiring board and the 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, or the like can be used when forming the laminated plate or the metal foil-clad laminated plate. In addition, in the molding (lamination molding) of a laminate or a metal foil-clad laminate, the temperature is generally 100 to 300 ° C., the surface pressure is ^{2 to} 100 kgf / cm ² , and the heating time is generally 0.05 to 5 hours. Is. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Especially when a multi-stage press is used, from the viewpoint of sufficiently promoting the curing of the prepreg, the temperature is preferably 200 to 250 ° C., the pressure is 10 to 40 kgf / cm ² , and the heating time is preferably 80 to 130 minutes, and the temperature is 215 ° C. or higher. More preferably, the temperature is 235 ° C, the pressure is 25 to 35 kgf / cm ² , and the heating time is 90 minutes to 120 minutes. It is also possible to form a multilayer board by combining the above-mentioned prepreg and a separately prepared wiring board for the inner layer and performing lamination molding.

[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 prepreg. For example, by forming a predetermined wiring pattern on the metal foil-clad laminate of the present embodiment described above, it can be suitably used as a printed wiring board. As described above, the metal foil-clad laminate of the present embodiment does not have a clear glass transition temperature (Tg-less) and tends to sufficiently reduce warpage (achieve low warpage). It can be used particularly effectively as a printed wiring board that requires such performance.

  Specifically, the printed wiring board of the present embodiment can be manufactured by the following method, for example. First, the metal foil-clad laminate (copper-clad laminate, etc.) described above is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to form an inner layer substrate. The inner layer circuit surface of this inner layer substrate is subjected to a surface treatment to increase the adhesive strength if necessary, then the required number of the above prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is further provided on the outer side thereof. They are laminated, heated and pressed, and integrally molded (laminated). In this way, a multilayer laminate having an insulating layer formed of a base material and a cured product of a thermosetting resin composition between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. The method of laminating and the forming conditions thereof are the same as those of the above-mentioned laminated board or metal foil-clad laminated board. Then, after performing a drilling process for through holes and via holes in this multilayer laminated plate, desmear treatment is performed to remove smear which is a residue of resin 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 electrically connect the inner layer circuit and the outer layer circuit metal foil, and then the outer layer circuit metal foil is etched to form the outer layer circuit, and the printed wiring board is manufactured. To be done.

  In this case, for example, the above-mentioned prepreg (base material and the above-mentioned resin composition attached thereto) constitutes an insulating layer.

  When the metal foil-clad laminate is not used, a printed wiring board may be prepared by forming a conductor layer to be a circuit on the prepreg. At this time, a method of electroless plating may be used to form the conductor layer.

  Further, as shown in FIG. 9, the printed wiring board of the present embodiment has a first insulating layer (1) formed of at least one or more of the above-mentioned prepregs, and the first insulating layer (1). ), A plurality of insulating layers including at least one or more second insulating layers (2) formed of the above-mentioned prepregs laminated in one surface direction (lower surface direction in the drawing), and the plurality of insulating layers (1, 2). ), A plurality of first conductor layers (3) disposed between the first conductor layer (3) and a second conductor layer (3) disposed as an outermost layer of the plurality of insulating layers (1, 2). It is preferable to have a conductor layer. According to the knowledge of the inventors, in a normal laminated board, for example, a multilayer printed wiring board is formed by laminating another prepreg in both surface directions of a prepreg which is one core substrate. The prepreg of the embodiment is a coreless type manufactured by laminating another prepreg forming the second insulating layer (2) only on one side of the one prepreg forming the first insulating layer (1). It was confirmed to be particularly effective for the multilayer printed wiring board (multi-layer coreless substrate).

  In other words, the prepreg and the resin composition of the present embodiment can effectively reduce the amount of warpage when used in a printed wiring board, and are not particularly limited, but among printed wiring boards, they are multi-layered. It is particularly effective for coreless substrates. That is, a general printed wiring board generally has a symmetrical structure on both sides and thus tends to be hard to warp, whereas a multilayer coreless substrate tends to have an asymmetrical structure on both sides, and thus is more likely to warp than an ordinary printed wiring board. There is a tendency. Therefore, by using the prepreg and the resin composition of the present embodiment, it is possible to particularly effectively reduce the amount of warpage of the multilayer coreless substrate, which conventionally tends to warp.

  In addition, in FIG. 9, a configuration in which two sheets of the second insulating layer (2) are laminated on one sheet of the first insulating layer (1) (that is, a configuration in which the plurality of insulating layers is three layers) is shown. Although shown, the number of second insulating layers (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, the prepreg satisfying the numerical ranges of the physical parameters relating to the mechanical properties (storage elastic modulus and loss elastic modulus) represented by the formulas (1) to (5), preferably the formulas (1A) to (5A), is described above. In the printed wiring board of the present embodiment having the configuration, particularly in the multilayer coreless substrate, there is no clear glass transition temperature (less Tg), and the warp can be sufficiently reduced (low warp is achieved). It can be used particularly effectively as a printed wiring board and a multilayer coreless board.

  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 compound (SN495VCN) In a reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.): The repeating unit number n of naphthol aralkyl includes those having a repeating unit number of 1 to 5.) 0.47 mol (in terms of OH group) was dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at −10 ° C., 300 g of 0.93 mol of cyanogen chloride in chloroform was dropped into the reactor over 1.5 hours, and after the dropping was completed, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor and stirred for 30 minutes to complete the reaction. By-produced triethylamine hydrochloride was filtered off from the reaction solution, and 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 degassed under reduced pressure at 90 ° C. to give a brown solid α-naphtholaralkyl cyanate compound represented by the above formula (15) (in the formula: R ^{6 of} are all hydrogen atoms). When the obtained α-naphthol aralkyl type cyanate ester compound was analyzed by infrared absorption spectrum, absorption of a cyanate ester group was confirmed at around 2264 cm ⁻¹ .

[Example 1]
Maleimide compound (A) (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide equivalent 186 g / eq.) 45 parts by mass, allyl group-containing compound (B) and alkenyl-substituted nadiimide compound (E) (BANI-M, Maruzen) Petrochemical Co., Ltd., allyl equivalent: 286 g / eq., 34 parts by mass, epoxy resin (C) consisting of bisphenol A type structural unit and hydrocarbon type structural unit (EPICLON EXA-4850-150, manufactured by DIC Corporation) , Epoxy equivalent: 450 g / eq.) 10 parts by mass, 1-part by mass of the α-naphthol aralkyl type cyanate ester compound (SN495VCN, cyanate equivalent: 261 g / eq.) Of Synthesis Example 1 which is a cyanate ester compound (F), Epoxy compound (G) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 320 g / q.) 10 parts by mass, 120 parts by mass of slurry silica (SC-2050MB, manufactured by Admatechs Co., Ltd.) which is a filler (H), and the same silicone composite powder (KMP-600, manufactured by Shin-Etsu Chemical Co., Ltd.) 20. Parts by mass, silane coupling agent (Z-6040, manufactured by Toray Dow Corning Co., Ltd.) 5 parts by mass, wetting dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) 1 part by mass, and curing accelerator 0.5 parts by mass of triphenylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.1 parts by mass of zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) are mixed and diluted with methyl ethyl ketone to produce a varnish. Got This varnish was impregnated and coated on E glass woven fabric (IPC # 2116, manufactured by Arisawa Seisakusho Co., Ltd.) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 57% by volume.

[Example 2]
The varnish obtained in Example 1 was impregnated and coated on an E glass woven cloth (IPC # 1030, manufactured by Unitika Ltd.) and dried by heating at 160 ° C. for 3 minutes to prepare a prepreg having a resin composition content of 73% by volume. Obtained.

[Example 3]
From 43 parts by mass of the maleimide compound (A) (BMI-2300), 32 parts by mass of the allyl group-containing compound (B) and the alkenyl-substituted nadiimide compound (E) (BANI-M), the bisphenol A type structural unit and the hydrocarbon type structural unit. Α-naphthol aralkyl-type cyanic acid of Synthesis Example 1, which is an epoxy resin (C) (EPICLON EXA-4816, manufactured by DIC Corporation, epoxy equivalent: 403 g / eq.), And a cyanate ester compound (F) 5 parts by mass of an ester compound (SN495VCN), 10 parts by mass of an epoxy compound (G) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 320 g / eq.), And slurry silica (SC) as a filler (H). -2050MB) 100 parts by mass, the same slurry silica (SC-5050MOB, Admatex Co., Ltd.) ) 100 parts by mass, and the same silicone composite powder (KMP-600) 20 parts by mass, silane coupling agent (Z-6040) 5 parts by mass, wetting dispersant (DISPERBYK-111, manufactured by Big Chemie Japan KK) 2 parts by mass. Parts and the same (DISPERBYK-161) 1 part by mass, and 0.5 parts by mass of triphenylimidazole which is a curing accelerator and 0.1 parts by mass of zinc octylate are mixed and diluted with methyl ethyl ketone to obtain a varnish. It was An E glass woven fabric (IPC # 2116) was impregnated with this varnish and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 57% by volume.

[Example 4]
An E glass woven fabric (IPC # 1030) was impregnated with the varnish obtained in Example 3 and heat-dried at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Comparative Example 1]
Synthesis Example 1 which is 51 parts by mass of maleimide compound (A) (BMI-2300), 38 parts by mass of allyl group-containing compound (B) and alkenyl-substituted nadiimide compound (E) (BANI-M), and cyanate ester compound (F). 1 part by mass of α-naphthol aralkyl type cyanate ester compound (SN495VCN), 10 parts by mass of epoxy compound (G) (NC-3000FH), 120 parts by mass of slurry silica (SC-2050MB) as a filler (H), and 20 parts by mass of the same silicone composite powder (KMP-600), 5 parts by mass of a silane coupling agent (Z-6040), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161), and triphenylimidazole as a curing accelerator 0. 5 parts by mass and 0.1 part by mass of zinc octylate are mixed, and methyl ethyl ketone is added. To obtain a varnish by interpretation. An E glass woven fabric (IPC # 2116) was impregnated with this varnish and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 57% by volume.

[Comparative Example 2]
E glass woven fabric (IPC # 1030) was impregnated with the varnish obtained in Comparative Example 1 and heat-dried at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Comparative Example 3]
Synthesis Example 1 which is 49 parts by mass of maleimide compound (A) (BMI-2300), 36 parts by mass of allyl group-containing compound (B) and alkenyl-substituted nadiimide compound (E) (BANI-M), and cyanate ester compound (F). 5 parts by mass of α-naphthol aralkyl cyanate ester compound (SN495VCN), 10 parts by mass of epoxy compound (G) (NC-3000FH), 100 parts by mass of slurry silica (SC-2050MB) as a filler (H), and 100 parts by mass of slurry silica (SC-5050MOB), 20 parts by mass of the same silicone composite powder (KMP-600), 5 parts by mass of silane coupling agent (Z-6040), 2 parts by mass of wetting and dispersing agent (DISPERBYK-111), and 1 part by mass of the same (DISPERBYK-161) and a curing accelerator. It was mixed 0.5 part by weight Li-phenylimidazole and the zinc octoate 0.1 parts by weight, to obtain a varnish by diluting with methyl ethyl ketone. An E glass woven fabric (IPC # 2116) was impregnated with this varnish and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 57% by volume.

[Comparative Example 4]
E glass woven fabric (IPC # 1030) was impregnated with the varnish obtained in Comparative Example 3 and heat-dried at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Comparative Example 5]
15 parts by mass of maleimide compound (BMI-70, manufactured by KAI Kasei Co., Ltd., maleimide equivalent: 221 g / eq.), Cyanate ester compound (F), α-naphtholaralkyl-type cyanate ester compound of Synthesis Example 1 (SN495VCN) 35 parts by mass, epoxy compound (G) (NC-3000FH) 50 parts by mass, filler (H) slurry silica (SC-2050MB) 100 parts by mass, the same slurry silica (SC-5050MOB) 100 parts by mass. And 20 parts by mass of the same silicone composite powder (KMP-600), 5 parts by mass of a silane coupling agent (Z-6040), 2 parts by mass of a wetting and dispersing agent (DISPERBYK-111) and 1 part by mass of the same (DISPERBYK-161), and 0.5 parts by mass of triphenylimidazole, which is a curing accelerator, and It was mixed 0.1 part by weight chill zinc, to obtain a varnish by diluting with methyl ethyl ketone. An E glass woven fabric (IPC # 2116) was impregnated with this varnish and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 57% by volume.

[Comparative Example 6]
An E glass woven fabric (IPC # 1030) was impregnated with the varnish obtained in Comparative Example 5 and heat-dried at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Physical property evaluation]
Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, samples for measuring and evaluating physical properties were prepared by the procedures shown in the following items, and mechanical properties (storage elastic modulus and loss elastic modulus) were measured, The physical property parameters regarding the mechanical properties in the formulas (1) to (5) and the formulas (1A) to (5A), the glass transition temperature (Tg), the warp amount (two types), and the substrate shrinkage ratio before and after the reflow process were measured and evaluated. The results of Examples are collectively shown in Table 1, and the results of Comparative Examples are collectively shown 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 6, 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 a predetermined insulating layer thickness. The obtained copper foil-clad laminate was cut into a size of 5.0 mm × 20 mm with a dicing saw, and then the surface copper foil was removed by etching to obtain a measurement sample. Using this measurement sample, the mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ″) were measured by the DMA method using a dynamic viscoelasticity analyzer (TA Instruments) according to 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 6, 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 a predetermined insulating layer thickness. The obtained copper foil-clad laminate was cut into a size of 12.7 mm × 2.5 mm with a dicing saw, 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 using a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481 (average value of n = 3).

[Amount of warp: Bimetal method]
First, copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) was arranged on both upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and pressure was 30 kgf /. Lamination molding (thermosetting) was carried out for 120 minutes at a temperature of 220 ° C. and a cm ² to obtain a copper foil-clad laminate. Next, the copper foil was removed from the obtained copper foil-clad laminate. Next, one sheet of the prepreg obtained in each of Examples 1 to 4 and Comparative Examples 1 to 6 was further arranged on one surface of the laminated sheet from which the copper foil was removed, and the copper foil (3EC-VLP, Mitsui) was formed on both upper and lower surfaces thereof. Metal Mining Industry Co., Ltd., thickness 12 μm) was placed, and lamination molding (thermosetting) 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 copper foil was removed from the obtained copper foil-clad laminate to obtain a laminate. Then, a 20 mm × 200 mm strip-shaped plate was cut out from the obtained laminated plate, and the surface of the second prepreg was faced up, and the maximum value of the warp amount at both ends in the longitudinal direction was measured with a metal ruler. The average value was defined as the "warpage amount" by the bimetal method.

[Amount of warpage: multilayer coreless substrate]
First, as shown in FIG. 1, a carrier copper foil surface of an ultra-thin copper foil with a carrier (b1) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 μm) is formed on both surfaces of a prepreg to be a support (a). The prepreg (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 is further arranged on the side, and the copper foil (d) (3EC-VLP, Mitsui Mining & Smelting Co., Ltd. (Manufactured by Co., Ltd., thickness 12 μm) is further placed, and lamination molding is 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, for example, as shown in FIG. 3, to form a conductor layer (d ′). Next, as shown in FIG. 4, the prepreg (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 was placed on the laminated plate shown in FIG. 3 on which the conductor layer (d ′) was formed. Then, an ultra-thin copper foil with carrier (b2) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 μm) is further arranged thereon, and laminated molding is performed at a pressure of 30 kgf / cm ² and a temperature of 230 ° C. for 120 minutes. Then, the copper foil-clad laminate shown in FIG. 5 was obtained.

  Then, in the copper foil-clad laminate shown in FIG. 5, the carrier copper foil and the carrier ultra-thin copper foil (b1) with the carrier arranged on the support (a) (cured support prepreg) are peeled off. As a result, as shown in FIG. 6, the two laminated plates were peeled from the support (a), and further the carrier copper foil was peeled from the ultrathin copper foil with a carrier (b2) on the upper part of each laminated plate. . Next, processing was performed by a laser processing machine on the upper and lower ultra-thin copper foils of each obtained laminated plate, and as shown in FIG. 7, a predetermined via (v) was formed by chemical copper plating. Then, for example, as shown in FIG. 8, a conductor layer was formed by etching into a predetermined wiring pattern to obtain a panel (size: 500 mm × 400 mm) of a multilayer coreless substrate. The amount of warpage at the four corners and the central portion of the four sides of the obtained panel at a total of eight locations was measured with a metal gauge, and the average value was defined as the “amount of warpage” 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 6, 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 uniformly in a grid pattern at 9 points, 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). Then, the laminated plate was subjected to a reflow treatment with a salamander reflow device at a maximum temperature of 260 ° C. Then, the distance between the holes in the laminate was measured again (distance B). Then, the measured distances i and b were substituted into the following formula (I) to obtain the dimensional change rate of the substrate in the reflow process, and the value was used as the substrate shrinkage rate before and after the reflow process.
((Distance a)-(distance b)) / distance a × 100 ... Formula (I)

  The prepreg of this 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. 2016-255270 filed on December 28, 2016, and the contents of the description are incorporated herein.

Claims (10)

A thermosetting resin, and a resin composition containing a filler,
It said resin composition contains an E glass fabric as a substrate, and a 57 vol% to 73 vol% content of the resin composition, thermally cured under conditions of 230 ° C. and 100 minutes The resulting cured product has the following formulas (1) to (5);
E ′ (200 ° C.) / E ′ (30 ° C.) ≦ 0.90 (1)
E ′ (260 ° C.) / E ′ (30 ° C.) ≦ 0.85 (2)
E ′ (330 ° C.) / E ′ (30 ° C.) ≦ 0.80 (3)
E ″ max / E ′ (30 ° C.) ≦ 3.0% (4)
E ″ min / E ′ (30 ° C.) ≧ 0.5% (5)
(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. And 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.)
Satisfies the numerical range of physical property parameters related to mechanical properties,
Resin composition. Formula (6A) below;
E ′ (30 ° C.) ≦ 30 GPa (6A)
(In the formula, E ′ represents the storage elastic modulus of the cured product at the temperature shown in parentheses.)
Further satisfy the mechanical characteristics represented by,
The resin composition according to claim 1. The thermosetting resin is a maleimide compound (A), an allyl group-containing compound (B), an epoxy resin (C) comprising a bisphenol A type structural unit and a hydrocarbon type structural unit, a cyanate ester compound (F), and an epoxy. At least one selected from the group consisting of compound (G),
The resin composition according to claim 1 or 2 . The filler contains at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride,
Resin composition according to any one of claims 1-3. A cured product obtained by curing the resin composition according to any one of claims 1 to 4. An insulating layer comprising the resin composition according to claim 1 and an organic base material. An insulating layer comprising a substrate and a cured product of the resin composition according to claim 1. The insulating layer according to claim 6 or 7, wherein at least one sheet is laminated,
A metal foil disposed on one or both sides of the insulating layer,
A metal foil-clad laminate. An insulating layer according to claim 6 or 7,
A conductor layer formed on the surface of the insulating layer,
Printed wiring board having. A plurality of insulating layers according to claim 6 or 7,
A plurality of conductor layers including a first conductor layer arranged between each of the plurality of insulating layers, and a second conductor layer arranged on the surface of the outermost layer of the plurality of insulating layers;
Multilayer printed wiring board having.