JP2019048990A - Prepreg, laminate sheet, metal foil-clad laminate sheet, printed wiring board, and multilayer printed wiring board - Google Patents

Abstract

To provide a prepreg or the like not having a clear glass-transition temperature (Tg-less), and capable of reducing sufficiently warpage of a printed wiring board (attaining low warpage).SOLUTION: A prepreg includes a thermosetting resin, a filler and a substrate. A cured product obtained by thermally curing the prepreg under a condition of 230°C and 100 minutes satisfies following formulas (1)-(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) (E':storage modulus, E'': loss modulus, E'': loss modulus).SELECTED DRAWING: None

Description

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

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

  As one of the measures, low thermal expansion of the insulating layer used for a printed wiring board is mentioned. This is a method for suppressing the warpage by bringing the thermal expansion coefficient of the printed wiring board close to the thermal expansion coefficient of the semiconductor element, and is actively addressed at present (for example, see Patent Documents 1 to 3).

  As a method for suppressing the warpage of the semiconductor plastic package, besides increasing the thermal expansion of the printed wiring board, increasing the rigidity of the laminate (increasing the rigidity) or raising the glass transition temperature of the laminate (high Tg) Are being studied (see, for example, Patent Documents 4 and 5).

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

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

  That is, according to the present invention, a clear glass transition temperature (Tg) does not exist (so-called no Tg), and warpage of a printed wiring board, particularly, a multilayer coreless substrate can be sufficiently reduced (a low warpage is achieved). It is an object of the present invention to provide a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have conventionally found that the cured product of a prepreg has a larger thermal storage modulus with respect to the warpage behavior of a printed wiring board for a semiconductor plastic package. And although resin compositions capable of achieving higher elastic modulus retention rates have been considered effective, it has been found that this is not always the case. Furthermore, as a result of intensive researches, the present inventors have found that, in physical property parameters regarding a specific mechanical property in a cured product obtained by heat curing a prepreg, 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 the thermal storage elastic modulus and loss elastic modulus of a cured product obtained by thermally curing a prepreg satisfying a specific condition range, and the present invention has been completed.

That is, the present invention is as follows.
[1]
Thermosetting resin,
Filler,
A substrate,
A prepreg containing
A cured product obtained by thermally curing the prepreg under conditions of 230 ° C. and 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 indicated in the parentheses, and E′′max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. E ′ ′ min represents the minimum value of loss modulus of the cured product in the temperature range of 30 ° C. to 330 ° C.)
Meet the numerical range of physical property parameters related to mechanical characteristics
Prepreg.

[2]
Following formula (6A);
E ′ (30 ° C.) ≦ 30 GPa (6A)
(Wherein, 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 as described in [1].

[3]
The substrate is a glass substrate,
The prepreg as described in [1] or [2].

[4]
The glass substrate is made 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]
It has the prepreg in any one of [1]-[4] laminated | stacked on at least 1 sheet,
Laminated board.

[6]
A prepreg according to any one of [1] to [4] laminated at least one sheet;
Metal foils disposed on one side or both sides of the prepreg;
A metal foil-clad laminate having

[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.

[8]
A first insulating layer formed of the prepreg according to any one of [1] to [4] laminated at least one or more, and at least one or more laminated in one surface direction of the first insulating layer A plurality of insulating layers consisting of a second insulating layer formed of the prepreg according to any one of [1] to [4],
A plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers, and a second conductor layer disposed on the surface of the outermost layer of the plurality of insulating layers;
Multilayer printed wiring board.

  According to the present invention, a printed wiring board, in particular, a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring capable of sufficiently reducing the warpage of the multilayer coreless substrate (to achieve low warpage). Can provide a board.

It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board (however, the manufacturing method of a multilayer coreless board 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 a procedure of producing a panel of a multilayer coreless substrate. It is a process flow figure showing an example of a procedure of producing a panel of a multilayer coreless substrate. It is a process flow figure showing an example of a procedure of producing a panel of a multilayer coreless substrate. It is a process flow figure showing an example of a procedure of producing a panel of a multilayer coreless substrate. It is a process flow figure showing an example of a procedure of producing a panel of a multilayer coreless substrate. It is a process flow figure showing an example of a procedure of producing a panel of a multilayer coreless substrate. It is a process flow figure showing an example of a procedure of producing a panel of a multilayer coreless substrate. It is a fragmentary sectional view showing composition of an example of a panel of a multilayer coreless substrate.

  Hereinafter, although the form (henceforth "this embodiment") for carrying out the present invention is explained in detail, the present invention is not limited to this, and various modifications are possible in the range which does not deviate from the gist. It is possible. In the present embodiment, “resin solid content” refers to components excluding a solvent and a filler in a resin composition, unless otherwise noted, and “resin solid content 100 parts by mass” means resin It shall mean that the sum total of the solvent in the composition and the components excluding the filler is 100 parts by mass.

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

  Moreover, the prepreg of this embodiment is a numerical value range of the physical property parameter regarding the mechanical property in which the hardened | cured material obtained by thermosetting it on 230 degreeC and the conditions for 100 minutes is represented by following formula (1)-(5) And preferably satisfy the numerical range of 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 the parentheses, and E′′max is the maximum value of loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. E ′ ′ min represents the minimum value of loss modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. (E ′ ′ represents the loss modulus of the cured product).

  Conventionally, with regard to the warping behavior of printed wiring boards, it has been considered effective that a resin composition capable of achieving a larger heat storage elastic modulus and a higher elastic modulus maintenance factor in a cured product of a prepreg, The values of physical property parameters regarding the mechanical properties of the cured product obtained by thermally curing the prepreg under the conditions of 230 ° C. and 100 minutes are not necessarily the above-mentioned formulas (1) to (5), preferably the formula (1A) to By being within the range of (5A), the glass transition temperature (Tg) can be sufficiently raised, and the warpage of the laminate, the metal foil-clad laminate, the printed wiring board, particularly the multilayer coreless substrate itself is sufficient. It is possible to reduce the

  In other words, the numerical values of the physical property parameters regarding the mechanical properties of the cured product obtained by thermally curing the prepreg under the conditions of 230 ° C. and 100 minutes are preferably the above formulas (1) to (5), preferably formulas (1A) to (5A) Within the range of (1), there is preferably no clear glass transition temperature (without Tg), and warpage of the printed wiring board (particularly, multilayer coreless substrate) is sufficiently reduced (a low warpage is achieved). It becomes possible. That is, it can be said that satisfying formulas (4) and (5) relating to loss elastic modulus, preferably formulas (4A) and (5A) is synonymous with the absence of a clear glass transition temperature (Tg) (Tg-less) However, the cured product satisfies only the formulas (4) and (5), preferably the formulas (4A) and (5A), but 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 stretch, when it is used as a printed wiring board, the difficulty of its stretching suffers and it becomes 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 tend to be difficult to stretch due to the absence of Tg, and to make it easy to achieve low warpage of the printed wiring board.

  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 the formula (6B) is there.

E ′ (30 ° C.) ≦ 30 GPa (6A)
E ′ (30 ° C.) ≦ 25 GPa (6)
1 GPa ≦ E ′ (30 ° C.) (6 B)
Here, in formula, E 'shows the storage elastic modulus of the said hardened | cured material in the temperature shown in a parenthesis. That is, the prepreg of the present embodiment preferably has an E ′ (30 ° C.) of 30 GPa or less, more preferably 25 GPa or less. The lower limit value of E ′ (30 ° C.) is not particularly limited, but is preferably 1 GPa or more.

  If the mechanical properties of the cured product obtained by thermally curing the prepreg under conditions of 230 ° C. and 100 minutes are within the range of the above formula (6), it is possible to further reduce the warpage of the multilayer coreless substrate, in particular. Become.

The measuring method of the mechanical property (storage elastic modulus E 'and loss elastic modulus E'') of the hardened | cured material of a prepreg is not specifically limited, For example, it can measure by the following method. That is, copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is disposed on the upper and lower surfaces of one prepreg, and laminated for 100 minutes at a temperature of 230 ° C. and a pressure of 30 kgf / cm ² ) To obtain a copper-clad laminate having a predetermined insulating layer thickness. Next, the obtained copper foil-clad laminate is cut into a size of 5.0 mm × 20 mm with a dicing saw, and the copper foil on the surface is removed by etching to obtain a measurement sample. Using this measurement sample, measure the mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ′ ′) by DMA method with a dynamic viscoelastic analyzer (manufactured by TA Instruments) according to 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. More preferably, it is 40 to 80% by volume. When the content of the resin composition is in the above range, the moldability tends to be further improved.

  The substrate is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used according to the intended application and performance. Examples of the substrate include glass substrates, inorganic substrates other than glass, organic substrates and the like, and among these, glass substrates are particularly preferable from the viewpoint of high rigidity and heating dimensional stability. . Specific examples of fibers constituting these substrates are not particularly limited, and for glass substrates, for example, from E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass And at least one glass fiber selected from the group consisting of Moreover, as inorganic substrates other than glass, inorganic fibers other than glass, such as quartz, may be mentioned. Furthermore, in organic base materials, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4 'oxydiphenylene terephthalamide (TECHNOLA (registered trademark), Teijin Techno Products Limited) And wholly aromatic polyamides such as 2, 6-hydroxynaphthoic acid and parahydroxybenzoic acid (Bectran (registered trademark), manufactured by Kuraray Co., Ltd.), polyesters such as Zexion (registered trademark, manufactured by KB Salen), etc .; Organic fibers such as phenylene benzoxazole (Zyrone (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide and the like can be mentioned. These substrates may be used alone or in combination of two or more.

The shape of the substrate is not particularly limited, and examples thereof include woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat and the like. The weave method of the woven fabric is not particularly limited, but, for example, plain weave, lanyard weave, twill weave and the like are known, and these known ones can be appropriately selected and used according to the intended use and performance. . In addition, those obtained by opening these fibers, and glass woven fabrics which are surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the substrate are not particularly limited, but usually, those having about 0.01 to 0.3 mm are suitably 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 consisting of E glass, S glass, and T glass glass fibers More preferable.

[Resin composition]
The resin composition of the present embodiment used for the above-mentioned prepreg is not particularly limited as long as it contains a thermosetting resin and a filler, and, for example, a maleimide compound (A) and an allyl group-containing compound (B) And an epoxy resin (C) composed of a bisphenol A structural unit and a hydrocarbon 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. A laminate, a metal foil-clad laminate, a printed wiring board, especially a multilayer coreless substrate using a prepreg containing such a resin composition and a base material tends to be able 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-phenyl maleimide, N-hydroxyphenyl maleimide, 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 And 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 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 is further reduced, and the heat resistance and the glass transition temperature (Tg) tend to be further improved.

Here, in Formula (7), each R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (7), n ₁ represents an integer of 1 or more, preferably 10 or less, and more preferably 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 resin solid content. The amount is particularly preferably 35 to 50 parts by mass, and still more preferably 35 to 45 parts by mass. When the content of the maleimide compound (A) is in the above range, the thermal expansion coefficient of the obtained cured product is 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 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. Although it does not specifically limit as reactive functional groups other than an allyl group, For example, a cyanate group (cyanate ester group), a hydroxyl group, an epoxy group, an amine group, an isocyanate group, glycidyl group, and a phosphoric acid group are mentioned. 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 group) is more preferable. By having a hydroxyl group, a cyanate group (cyanate group) and an epoxy group, it has high flexural strength and flexural modulus, low dielectric constant, high glass transition temperature (high Tg), low thermal expansion coefficient, and thermal The conductivity tends to be further 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 the allyl group-containing compound (B) having a reactive functional group other than two or more allyl groups is used in combination, the reactive functional groups other than the allyl group may be the same or different. Among these, 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) in combination, flexural strength, flexural modulus, glass transition temperature (Tg) and thermal conductivity tend to be further improved.

  Among the above, it is preferable to use, as the allyl group-containing compound (B), an allyl group containing compound having a reactive functional group other than an allyl group and / or an alkenyl-substituted nadiimide compound (E) described later. 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.

  In addition, it is particularly preferable to use an allylphenol derivative (D) and / or an alkenyl-substituted nadiimide 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), 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 with respect to 100 parts by mass of resin solid content. Part, particularly preferably 25 to 40 parts by mass. When the content of the allyl group-containing compound (B) is in the above range, the flexibility, flexural strength, flexural modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and flexibility of the obtained cured product are obtained. The 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, and, for example, a bisphenol in which a hydrogen atom of the aromatic ring is substituted with an allyl group And a modified bisphenol compound in which the hydrogen atom of the aromatic ring is substituted with an allyl group, and the phenolic hydroxyl group is modified with a reactive functional group other than a hydroxyl group in reactive functional groups other than the above-mentioned allyl group, Specifically, compounds represented by the following formula (8) can be mentioned, and more specifically, diallyl bisphenol A, a cyanate ester compound of diallyl bisphenol A, and diallyl bisphenol A type epoxy can be mentioned.

  In formula (8), each Ra independently represents 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 allyl phenol derivative (D), bending strength, flexural modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and copper foil peel strength tend to be further improved.

  The above bisphenols are not particularly limited. For example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P And bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, bisphenol A is preferable.

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

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

  The preferred range of the content of the allylphenol derivative (D) conforms to the content of the allyl group-containing compound (B) described above.

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

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

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

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

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

  A commercial thing can also be used for an alkenyl substituted nadiimide compound (E). As what is marketed, although not particularly limited, for example, BANI-M (manufactured by Maruzen Petrochemical Co., Ltd., a compound represented by the formula (12)), BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.), And the like) and the like. 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. Still 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 with respect to 100 parts by mass of the resin solid content, and more preferably Is 35 to 45 parts by mass. When the content of the alkenyl-substituted nadiimide 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) consisting of bisphenol A structural unit and hydrocarbon structural unit]
The epoxy resin (C) comprising a bisphenol A structural unit and a hydrocarbon structural unit is a compound having one or more bisphenol A structural units and one or more hydrocarbon structural units in the molecule. It is not particularly limited. Among these, the compound represented by the following formula (14) is preferable. By using an epoxy resin (C) composed of such a bisphenol A structural unit and a hydrocarbon structural unit, the storage elastic modulus E 'at the time of heating of the obtained cured product tends to be a value suitable for warpage suppression. 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 each independently represent a hydrogen atom, a methyl group or a chlorine atom Or a bromine atom, and X represents 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 A group or an alkylene group having 2 to 15 carbon atoms is shown, and n represents a natural number.

  A commercially available thing can also be used for the epoxy resin (C) which consists of a bisphenol A type structural unit and a hydrocarbon type structural unit which were mentioned above. As what is marketed, although not particularly limited, for example, EPICLON EXA-4850-150 (manufactured by DIC Corporation, a compound having a structure represented by the formula (14)), EPICLON EXA-4816 (DIC (strain) And compounds in which X in the formula (14) is an ethylene group). These may be used alone or in combination of two or more.

  The content of the epoxy resin (C) composed of a bisphenol A structural unit and a hydrocarbon 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 resin solid content. Part, more preferably 10 to 20 parts by mass. When the content of the epoxy resin (C) composed of the bisphenol A structural unit and the hydrocarbon structural unit is within the above range, the storage elastic modulus E 'at the time of heating of the obtained cured product is a value suitable for suppressing warpage Tend to be

[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-described allyl phenol derivative (D), and, for example, naphthol aralkyl type cyanate ester represented by the following formula (15) Novolak-type cyanate ester represented by formula (16), biphenylaralkyl-type cyanate ester, bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-disilane Anatobenzene, 1,4-disocyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-disocyanatonaphthalene, 1,4-disocyanatonaphthalene, 1,6-disocyanatonaphthalene, 1,8-disocyanate Anatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6- Licyanato naphthalene, 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. In the formula (15), n ₂ represents an integer of 1 or more. The upper limit of n ₂ is usually 10, preferably 6.

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

  Among these, the cyanate ester compound (F) is composed of a naphthol aralkyl type cyanate ester represented by the formula (15), a novolak cyanate ester represented by the formula (16), and a biphenyl aralkyl type cyanate ester It is preferable to include one or more selected from the group, and one or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (15) and novolac type cyanate ester represented by formula (16) More preferably, By using such a cyanate ester compound (F), a cured product which is more excellent in flame retardancy, higher in curability, and lower in thermal expansion coefficient tends to be obtained.

  It does not specifically limit as a manufacturing method of these cyanate ester compounds (F), A well-known method can be used as a synthesis | combining method of a cyanate ester compound. The known method is not particularly limited. For example, a method of reacting a phenol resin and cyanogen halide in an inert organic solvent in the presence of a basic compound, a salt of a phenol resin and a basic compound, water, The method of forming in the solution to contain, and then making the obtained salt and cyanogen halide interface reaction of a two phase system is mentioned.

  The phenol resin to be a raw material of these cyanate ester compounds (F) is not particularly limited, and for example, naphthol aralkyl type phenol resin, novolak type phenol resin, biphenyl aralkyl type phenol resin represented by the following formula (17) It 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. In the formula (17), n ₄ represents an integer of 1 or more. The upper limit of n ₄ is usually 10, preferably 6.

  The naphthol aralkyl type phenol resin represented by the formula (17) can be obtained by condensation of a naphthol aralkyl resin and a cyanic acid. The naphthol aralkyl type phenol resin is not particularly limited. For example, naphthols such as α-naphthol and β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, and 1,4- What is obtained by reaction with benzenes such as di (2-hydroxy-2-propyl) benzene is mentioned. 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 more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the resin solid content. It is 45 parts by mass, more preferably 20 to 35 parts by mass. When the content of the cyanate ester compound is in the above range, the heat resistance and the 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 structural unit and the hydrocarbon 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 having two or more epoxy groups in one molecule, for example, bisphenol A 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, tetrafunctional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolac type epoxy resin 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, 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 in the above range, the flexibility, copper foil peel strength, chemical resistance and desmear resistance of the resulting cured product tend to be further improved.

[Filler (H)]
The resin composition of the present embodiment may further contain a filler (H). Although it does not specifically limit as a filler (H), For example, an inorganic filler and an organic filler are mentioned, It is preferable to contain the inorganic filler among both, and an organic filler is used with an inorganic filler It is preferable. The inorganic filler is not particularly limited, and examples thereof include natural silica, fused silica, synthetic silica, amorphous silica, silica such as aerosol and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated product (aluminium hydroxide is heated 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 , Mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fiber (E glass, T glass, D glass, Glass fine powders such as S glass, Q glass etc.), 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, acrylic type powder, core shell type rubber powder, silicone resin powder, silicone rubber powder, silicone composite powder and the like. 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 inorganic fillers such as silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride. More preferably, it contains at least one selected from the group consisting of silica, alumina, and boehmite. Use of such a filler (H) tends to further improve the high rigidity and the low warpage of the obtained cured product.

  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, 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 in the above range, the high rigidity and the low warpage of the obtained cured product tend to be further improved.

[Silane coupling agent and wetting and dispersing agent]
The resin composition of the present embodiment may further contain a silane coupling agent and a wetting and dispersing agent. The inclusion of a silane coupling agent or a 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 generally used for the surface treatment of inorganic substances in general, for example, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ Aminosilane compounds such as aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylic silane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride and the like; phenylsilane compounds and the like. The silane coupling agent may be used alone or in combination of two or more.

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

[Other resins, etc.]
The resin composition of the present embodiment may, if necessary, be 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-described allyl group-containing compound (B). It may further contain one or more selected from the group consisting of benzoxazine compounds and compounds having a polymerizable unsaturated group. By containing such other resin etc., it exists in the tendency which copper foil peel strength, bending strength, a bending elastic modulus etc. of the hardened | cured material obtained improve more.

[Other allyl group-containing compounds]
Other allyl group-containing compounds are not particularly limited, and examples thereof include allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, diallyl maleate and the like. It 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. More preferably, it is 20-35 mass parts. 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 resulting cured product tend to be further improved.

[Phenol resin]
As the phenolic resin, generally known ones can be used as long as they are phenolic resins 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 novolac type Phenol resin, biphenylaralkyl 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, phenolaralkyl 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 can be used singly or in combination of two or more. By containing such a phenol resin, it tends to be excellent by the adhesiveness, flexibility, etc. of the hardened material obtained.

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

[Oxetane resin]
As the oxetane resin, those generally known can be used, and the type is not particularly limited. Specific examples thereof include alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3, 3-dimethyl oxetane, 3-methyl-3-methoxy methyl oxetane, 3, 3 '. -Di (trifluoromethyl) perfluoxetane, 2-chloromethyl oxetane, 3, 3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toho Gosei Co., Ltd.), OXT-121 (Toho Gosei Trade name) etc. These oxetane resins can be used alone or in combination of two or more. By containing such an oxetane resin, it tends to be excellent by the adhesiveness, flexibility, etc. of the hardened material obtained.

  The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. When the content of the oxetane resin is in the above-mentioned range, it tends to be more excellent due to the adhesion and flexibility of the obtained cured product.

[Benzoxazine compound]
As the benzoxazine compound, generally known compounds can be used as long as they are compounds 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) bisphenol F-type benzooxazine BF-BXZ (trade name of Konishi Chemical), bisphenol S-type benzooxazine BS-BXZ (product of Konishi Chemical Name) etc. These benzoxazine compounds can be used alone or in combination of two or more. By containing such a benzoxazine compound, the resulting cured product tends to be excellent in flame retardancy, heat resistance, low water absorption, low dielectric and the like.

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

[Compound having a polymerizable unsaturated group]
As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the type 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 a monohydric or polyhydric alcohol 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, bisphenol F type epoxy (meth) acrylate; benzocyclobutene resin; Scan) maleimide resins. The compound which has these unsaturated groups can be used 1 type or in mixture of 2 or more types. By containing a compound having such a polymerizable unsaturated group, the cured product obtained 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, still more preferably 3 to 90 parts by mass with respect 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 in the above range, the cured product obtained tends to be further excellent in heat resistance, toughness and the like.

[Hardening accelerator]
The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited. For example, 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, etc .; phenol, xylenol, cresol, resorcinol, catecho Phenols such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, etc. organic metal salts thereof Dissolved in a hydroxyl group-containing compound such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyltin oxide, other organic tin compounds such as alkyltin and alkyltin oxide, etc. Be Among these, triphenylimidazole is particularly preferable because it accelerates the curing reaction and tends to be 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 preparation of the resin composition is lowered, the handling property is further improved, and the impregnating property to the substrate described later tends to be further improved.

  The solvent is not particularly limited as long as it can dissolve part or all of the resin component in the resin composition, and examples thereof include ketones such as acetone, methyl ethyl ketone and methyl cellosolve; and aroma such as toluene and xylene Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and acetates thereof. The solvents may be used alone or in combination of two or more.

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

  Moreover, at the time of preparation of the resin composition of this embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as the resin in the resin composition can be dissolved. The specific example is as described above.

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

[Laminated board and metal foil clad laminated board]
The laminated board of this embodiment has the said prepreg of this embodiment laminated | stacked by at least 1 sheet. Further, the metal foil-clad laminate of the present embodiment includes the laminate of the present embodiment (that is, the above-described prepreg of the present embodiment laminated at least one sheet) and metal foils disposed on one side or both sides of the laminate. And (conductor layer). By using a prepreg that satisfies the numerical range of physical property parameters related to the mechanical properties (storage elastic modulus and loss elastic modulus) represented by the formulas (1) to (5) described above, preferably the formulas (1A) to (5A) The laminates of the embodiment and the metal foil-clad laminates do not have a clear glass transition temperature (Tg-less), and tend to be able 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 a rolled copper foil or an electrolytic copper foil is preferable. Moreover, the thickness of a conductor layer is although it does not specifically limit, 1-70 micrometers is preferable, More preferably, it is 1.5-35 micrometers.

The forming method of the laminate and the metal foil-clad laminate and the forming conditions thereof are not particularly limited, and general methods and conditions of a laminate for a printed wiring board and a multilayer board can be applied. For example, when forming a laminate or a metal foil-clad laminate, a multistage press, a multistage vacuum press, a continuous forming machine, an autoclave forming machine or the like can be used. Moreover, in the formation (lamination molding) of laminates or metal foil-clad laminates, the temperature is 100 to 300 ° C., the pressure is ^{2 to} 100 kgf / cm ² surface pressure, and the heating time is generally 0.05 to 5 hours. It is. Furthermore, if necessary, post curing can be performed at a temperature of 150 to 300 ° C. In particular, when a multistage press is used, the temperature is preferably 200 ° C. to 250 ° C., the pressure is 10 to 40 kgf / cm ² , the heating time is 80 minutes to 130 minutes, and the temperature is 215 ° C. The temperature is preferably 235 ° C., the pressure is 25 to 35 kgf / cm ² , and the heating time is 90 minutes to 120 minutes. Moreover, it is also possible to make it a multilayer board by carrying out lamination molding of the above-mentioned prepreg and the wiring board for inner layers prepared separately, and laminating-forming.

[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 above-mentioned prepreg. For example, it can use suitably as a printed wiring board by forming a predetermined | prescribed wiring pattern in the metal foil tension laminate board of this embodiment mentioned above. As described above, the metal foil-clad laminate of this embodiment does not have a clear glass transition temperature (Tg-less) and tends to sufficiently reduce warpage (achieves 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, for example, by the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate etc.) is prepared. The 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 the inner layer substrate is optionally subjected to a surface treatment to increase the adhesive strength, and then, the required number of the above-described prepregs are stacked on the inner layer circuit surface, and metal foil for the outer layer circuit is further outside. The layers are laminated, heated and pressurized, and integrally molded (laminated). In this manner, a multilayer laminate is produced in which an insulating layer made of a cured product of a base material and a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. The method of lamination molding and the molding conditions thereof are the same as those of the above-described laminated sheet or metal foil-clad laminated sheet. Next, after the multi-layer laminate is subjected to drilling for through holes and via holes, desmearing 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 the hole to electrically connect the inner layer circuit and the metal foil for the outer layer circuit, and the metal foil for the outer layer circuit is etched to form the outer layer circuit. Be done.

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

  Moreover, when a metal foil tension laminate sheet is not used, the conductor layer used as a circuit may be formed in the said prepreg, and a printed wiring board may be produced. At this time, a method of electroless plating can also be used to form the conductor layer.

  Furthermore, as shown in FIG. 9, the printed wiring board of the present embodiment is a first insulating layer (1) formed of the above-described prepreg on which at least one or more sheets are laminated, and the first insulating layer (1 A plurality of insulating layers (1 and 2) formed of the above-described prepregs laminated on at least one sheet in the direction of the lower surface of the drawing) and the plurality of insulating layers (1, 2) And a plurality of second conductor layers (3) disposed in the outermost layers of the plurality of insulating layers (1, 2). It is preferable to have a conductor layer. According to the findings of the present inventors, in a common laminate, for example, a multilayer printed wiring board is formed by laminating another prepreg in the both surface direction 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 in one direction of one prepreg forming the first insulating layer (1). It was confirmed that the method is particularly effective for the multilayer printed wiring board (multilayer coreless substrate) of

  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 is not particularly limited. It is particularly effective in coreless substrates. That is, a normal printed wiring board tends to be difficult to warp because it is generally symmetrical on both sides, whereas a multilayer coreless substrate tends to be asymmetrical on both sides, so it is easier to warp than a normal 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 has conventionally been prone to warpage.

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

  As described above, the prepreg satisfying the numerical range of the physical property parameters regarding the mechanical properties (storage elastic modulus and loss elastic modulus) represented by the above formulas (1) to (5), preferably, formulas (1A) to (5A) In the printed wiring board of the present embodiment having the configuration, in particular, a multilayer coreless substrate, no clear glass transition temperature exists (Tg-less), and warpage can be sufficiently reduced (low warpage can be achieved). It can be used particularly effectively as a printed wiring board and a multilayer coreless substrate.

  Hereinafter, the present invention will be more specifically described using examples and comparative examples. However, the present invention is not limited at all by the following examples.

Synthesis Example 1 Synthesis of α-Naphthol Aralkyl Type Cyanate Ester Compound (SN 495 VCN) In a reactor, α-Naphthol Aralkyl resin (SN 495 V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.): The number n of repeating units of naphthol aralkyl is from 1 to 5. 0.47 mol (in terms of OH group) is dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine is added to this solution. While maintaining the temperature at −10 ° C., 300 g of a chloroform solution of 0.93 mol of cyanogen chloride was dropped into the reactor over 1.5 hours, and after completion of the dropping, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further dropped into the reactor, and stirred for 30 minutes to complete the reaction. After filtering off the by-produced triethylamine hydrochloride from the reaction solution, the obtained filtrate was washed with 500 ml of 0.1 N hydrochloric acid, and then washing with 500 ml of water was repeated four times. The product is dried over sodium sulfate, evaporated at 75 ° C., and degassed under reduced pressure at 90 ° C. to obtain a brown solid α-naphthol aralkyl type cyanate ester compound represented by the above formula (15) All R ⁶ are 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 in the vicinity of 2264 cm ⁻¹ .

Example 1
Maleimide compound (A) (BMI-2300, manufactured by Daiwa Kasei Kogyo 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 An epoxy resin (C) (EPICLON EXA-4850-150, manufactured by DIC Corporation) comprising 34 parts by mass of an equivalent amount of allyl alcohol: 286 g / eq., A bisphenol A type structural unit and a hydrocarbon type structural unit, manufactured by Petrochemical Co., Ltd. 10 parts by mass of epoxy equivalent: 450 g / eq., 1 part by mass of α-naphthol aralkyl type cyanate ester compound (SN 495 VCN, equivalent of cyanate: 261 g / eq.) Of Synthesis Example 1 which is 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-2050 MB, manufactured by Admatex Co., Ltd.) as filler (H), and the same silicone composite powder (KMP-600, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 Parts by mass, 5 parts by mass of silane coupling agent (Z-6040, manufactured by Toray Dow Corning Co., Ltd.), 1 part by mass of wetting dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.), and curing accelerator Of 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.) I got This varnish was impregnated and coated on an E-glass woven fabric (manufactured by Arisawa Seisakusho, IPC # 2116) 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 is impregnated and coated on an E-glass woven fabric (manufactured by Unitika Co., Ltd., IPC # 1030), and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume. Obtained.

[Example 3]
43 parts by mass of maleimide compound (A) (BMI-2300), 32 parts by mass of allyl group-containing compound (B) and alkenyl-substituted nadiimide compound (E) (BANI-M), from bisphenol A structural unit and hydrocarbon structural unit 10 parts by mass of an epoxy resin (C) (EPICLON EXA-4816, manufactured by DIC Corporation, epoxy equivalent: 403 g / eq.), An α-naphtholaralkyl type cyanate of Synthesis Example 1 which is a cyanate compound (F) 5 parts by mass of an ester compound (SN 495 VCN), 10 parts by mass of an epoxy compound (G) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 320 g / eq.), Slurry silica (SC) as filler (H) -2050 MB) 100 parts by mass, the same slurry silica (SC-5050 MOB, Admatex Co., Ltd.) 100 parts by mass, and 20 parts by mass of the 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, manufactured by Big Chemie Japan Co., Ltd.) The varnish is obtained by mixing 1 part by mass of the same and (DISPERBYK-161), 0.5 parts by mass of triphenylimidazole as a curing accelerator and 0.1 parts by mass of zinc octylate and diluting with methyl ethyl ketone The This varnish was impregnated and coated onto E glass woven fabric (IPC # 2116), 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
The varnish obtained in Example 3 was impregnated and coated onto an E glass woven fabric (IPC # 1030), and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

Comparative Example 1
Synthetic Example 1 of 51 parts by mass of a maleimide compound (A) (BMI-2300), an allyl group-containing compound (B) and 38 parts by mass of an alkenyl substituted nadiimide compound (E) (BANI-M) and a cyanate ester compound (F) 1 part by mass of α-naphthol aralkyl type cyanate ester compound (SN 495 VCN), 10 parts by mass of epoxy compound (G) (NC-3000 FH), 120 parts by mass of slurry silica (SC-2050 MB) as 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 0. 3 parts of triphenylimidazole as a curing accelerator. Mix 5 parts by mass and 0.1 parts by mass of zinc octylate with methyl ethyl ketone To obtain a varnish by interpretation. This varnish was impregnated and coated onto E glass woven fabric (IPC # 2116), 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
The varnish obtained in Comparative Example 1 was impregnated and coated onto an E glass woven fabric (IPC # 1030), and dried by heating 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), allyl group-containing compound (B) and 36 parts by mass of alkenyl-substituted nadiimide compound (E) (BANI-M), cyanate ester compound (F) 5 parts by mass of α-naphthol aralkyl type cyanate ester compound (SN 495 VCN), 10 parts by mass of epoxy compound (G) (NC-3000 FH), 100 parts by mass of slurry silica (SC-2050 MB) as filler (H), 100 parts by mass of slurry silica (SC-5050 MOB), 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), 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. This varnish was impregnated and coated onto E glass woven fabric (IPC # 2116), 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
The varnish obtained in Comparative Example 3 was impregnated and coated on an E glass woven fabric (IPC # 1030), and dried by heating 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 a maleimide compound (BMI-70, manufactured by Kei I Kasei Co., Ltd., maleimide equivalent: 221 g / eq.), An α-naphtholaralkyl type cyanate ester compound of Synthesis Example 1 which is a cyanate ester compound (F) 35 parts by mass of (SN 495 VCN), 50 parts by mass of epoxy compound (G) (NC-3000 FH), 100 parts by mass of slurry silica (SC-2050 MB) as filler (H), 100 parts by mass of the same slurry silica (SC-5050 MOB) And 20 parts by mass of the silicone composite powder (KMP-600), 5 parts by mass of the silane coupling agent (Z-6040), 2 parts by mass of the wetting and dispersing agent (DISPERBYK-111), and 1 part by mass of the same (DISPERBYK-161), And 0.5 parts by mass of triphenylimidazole as a curing accelerator It was mixed 0.1 part by weight chill zinc, to obtain a varnish by diluting with methyl ethyl ketone. This varnish was impregnated and coated onto E glass woven fabric (IPC # 2116), 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
The varnish obtained in Comparative Example 5 was impregnated and coated onto an E glass woven fabric (IPC # 1030), and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Measurement of physical properties]
Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, samples for evaluation of physical properties were prepared according to the procedures shown in the following items, and mechanical properties (storage elastic modulus and loss elastic modulus), Physical property parameters relating to mechanical properties in formulas (1) to (5) and formulas (1A) to (5A), glass transition temperature (Tg), amount of warpage (two types), and substrate shrinkage before and after the reflow process were measured and evaluated. The results of Examples are summarized in Table 1, and the results of Comparative Examples are summarized in Table 2.

[Mechanical Properties]
Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is disposed on the upper and lower surfaces of one of the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and the pressure is 30 kgf / cm ² Then, lamination molding (heat curing) was carried out 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 the copper foil on the surface was removed by etching to obtain a measurement sample. Using this sample for measurement, the mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ′ ′) were measured by the DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481. (Average value of n = 3).

[Glass transition temperature (Tg)]
Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is disposed on the upper and lower surfaces of one of the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and the pressure is 30 kgf / cm ² Then, lamination molding (heat curing) was carried out 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 the copper foil on the surface was removed by etching to obtain a measurement sample. Using this measurement sample, the glass transition temperature (Tg) was measured by a dynamic viscoelasticity analyzer (manufactured by TA Instruments) according to JIS C6481 by a DMA method (average value of n = 3).

Warpage amount: bimetal method
First, copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is disposed on the upper and lower surfaces of one of the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and the pressure is 30 kgf / cm ^2, performs lamination molding for 120 minutes at a temperature 220 ° C. (heat curing), to give the DohakuCho laminate. Next, the copper foil was removed from the obtained copper foil-clad laminate. Next, one of the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6 is further disposed on one side of the laminate from which the copper foil has been removed, and the above copper foil (3EC-VLP, Mitsui Metal Mining Co., Ltd. product, thickness 12 μm) was disposed, and lamination molding (thermal curing) was performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate again. Furthermore, the said copper foil was removed from the obtained copper foil tension laminated board, and the laminated board was obtained. Then, a 20 mm × 200 mm strip is cut out from the obtained laminate, and the second laminated sheet is faced up, and the maximum value of the amount of warpage in the lengthwise direction is measured with a metal gauge. The average value was taken as the "warpage amount" by the bimetal method.

[Correction amount: multilayer coreless substrate]
First, as shown in FIG. 1, on both sides of the prepreg to be the support (a), the carrier copper foil surface of the carrier-attached ultrathin copper foil (b1) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 μm) is prepregged The prepreg (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 is further disposed on the side, and the copper foil (d) (3EC-VLP, Mitsui Metal Mining Co., Ltd.) is further disposed thereon. The thickness of 12 μm) was further disposed, and lamination molding was performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate shown in FIG.

Then, the copper foil (d) of the obtained copper foil-clad laminate shown in FIG. 2 was etched into a predetermined wiring pattern as shown in FIG. 3, for example, to form a conductor layer (d ′). Next, as shown in FIG. 4, the prepreg (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 is disposed on the laminate shown in FIG. 3 on which the conductor layer (d ′) is formed. The carrier-incorporated ultra thin copper foil with carrier (b2) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 μm) is further disposed, and lamination molding is performed at a pressure of 30 kgf / cm ² and a temperature of 230 ° C. for 120 minutes. Then, a copper foil-clad laminate shown in FIG. 5 was obtained.

  Next, in the copper foil-clad laminate shown in FIG. 5, the carrier copper foil and the ultra thin copper foil of the carrier-provided ultra thin copper foil (b1) disposed on the support (a) (cured support prepreg) are peeled off. Thus, as shown in FIG. 6, the two laminates were peeled from the support (a), and the carrier-coated copper foil was peeled from the carrier-attached ultrathin copper foil (b2) in the upper part of each laminate. . Next, the upper and lower ultra-thin copper foils of each of the obtained laminates were processed by a laser processing machine, and as shown in FIG. 7, predetermined vias (v) were formed by chemical copper plating. Then, for example, as shown in FIG. 8, a conductor layer was formed by etching in a predetermined wiring pattern, to obtain a panel (size: 500 mm × 400 mm) of a multilayer coreless substrate. Then, the amount of warpage at a total of eight points at the four corners and the four side central portions of the obtained panel was measured using a metal scale, and the average value was taken as the "warpage amount" of the panel of the multilayer coreless substrate.

[Substrate contraction rate before and after reflow process]
Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is disposed on the upper and lower surfaces of one of the prepregs 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, after the drilling process of nine points was uniformly performed to the obtained copper foil-clad laminate using a drill, the copper foil was removed.

Then, first, the distance between the holes in the laminate from which the copper foil was removed was measured (distance a). Next, the laminate was subjected to a reflow treatment at a maximum temperature of 260 ° C. in a salamander reflow device. Thereafter, the distance between the holes in the laminate was again measured (distance b). Then, the measured distances a and b are substituted into the following formula (I), the dimensional change rate of the substrate in the reflow process is determined, and the value is used as the substrate shrinkage rate before and after the reflow process.
((Distance a)-(distance b)) / distance i × 100 formula (I)

  The prepreg of this embodiment has industrial applicability as a material of 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 Dec. 28, 2016, the contents of which are incorporated herein by reference.

Claims (8)

Thermosetting resin,
Filler,
A substrate,
A prepreg containing
A cured product obtained by thermally curing the prepreg under conditions of 230 ° C. and 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 indicated in the parentheses, and E′′max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. E ′ ′ min represents the minimum value of loss modulus of the cured product in the temperature range of 30 ° C. to 330 ° C.)
Meet the numerical range of physical property parameters related to mechanical characteristics
Prepreg. Following formula (6A);
E ′ (30 ° C.) ≦ 30 GPa (6A)
(Wherein, 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 claim 1. The substrate is a glass substrate,
The prepreg according to claim 1 or 2. The glass substrate is made 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,
The prepreg according to claim 3. The prepreg according to any one of claims 1 to 4, wherein at least one sheet is laminated.
Laminated board. The prepreg according to any one of claims 1 to 4, wherein at least one sheet is laminated.
Metal foils disposed on one side or both sides of the prepreg;
A metal foil-clad laminate having An insulating layer formed of the prepreg according to any one of claims 1 to 4;
A conductor layer formed on the surface of the insulating layer,
Printed wiring board. The 1st insulating layer formed with the prepreg of any one of Claims 1-4 laminated | stacked by at least 1 sheet, and at least 1 sheet laminated in the single side | surface direction of said 1st insulating layer A plurality of insulating layers comprising a second insulating layer formed of the prepreg according to any one of claims 1 to 4;
A plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers, and a second conductor layer disposed on the surface of the outermost layer of the plurality of insulating layers;
Multilayer printed wiring board.