TWI656151B - Prepreg, laminated board, metal foil laminated board, printed circuit board, and multilayer printed circuit board - Google Patents

Abstract

In order to provide prepregs, laminates, and metal-clad laminates that do not have a clear glass transition temperature (no Tg) and that can sufficiently reduce the warpage of printed circuit boards, especially multilayer non-core substrates (to achieve low warpage) A board, a printed circuit board, and a multilayer printed circuit board. The prepreg of the present invention contains a thermosetting resin, a filler, and a substrate. In addition, the hardened material obtained by thermally curing the prepreg at 230 ° C and 100 minutes meets the following formulae (1) to (5); E '(200 ° C) / E' (30 ° C) ≦ 0.90… (1) E '(260 ℃) / E' (30 ℃) ≦ 0.85… (2) E '(330 ℃) / E' (30 ℃) ≦ 0.80… (3) E''max / E ' (30 ℃) ≦ 3.0% ... (4) E''min / E '(30 ℃) ≧ 0.5% ... (5) (E': storage elastic modulus, E '' loss elastic modulus, E '': Loss of elastic modulus).

Description

Prepreg, laminated board, metal foil-clad laminated board, printed circuit board, and multilayer printed circuit board

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

In recent years, semiconductor packages that are widely used in electronic equipment, communication equipment, personal computers, and the like have advanced in function and miniaturization. With this, the high integration and high-density mounting of various components used in semiconductor packages have accelerated in recent years. . Along with this, various characteristics required for a printed circuit board for a semiconductor package have become stricter. For the characteristics required for this printed circuit board, for example: low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric tangent, low thermal expansion coefficient, heat resistance, chemical resistance, high plating peel strength Wait. In addition, suppressing warpage of printed circuit boards, especially suppressing warpage of multilayer multilayer coreless substrates (to achieve low warpage) has recently become an important issue, and various countermeasures have been taken.

One of the countermeasures is to reduce the thermal expansion of the insulating layer used in the printed wiring board. This is a method of suppressing warpage by making the thermal expansion coefficient of a printed circuit board close to the thermal expansion coefficient of a semiconductor device, and has been actively adopted (for example, refer to Patent Documents 1 to 3).

As a method for suppressing the warpage of semiconductor plastic packages, in addition to the low thermal expansion of printed circuit boards, there have been discussions to improve the rigidity (high rigidity) of the laminated board and increase the glass transition temperature (high Tg of the laminated board). (See, for example, Patent Documents 4 and 5). [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2013-216884 Patent Document 2: Japanese Patent Application Publication No. 3173332 Patent Document 3: Japanese Patent Application Publication No. 2009-035728 Patent Document 4: Japanese Patent Application Publication No. 2013-001807 Patent Document 5: Japanese Patent Laid-Open No. 2011-178992

However, according to the detailed research by the inventors of the present case, even the above-mentioned conventional technologies are still unable to sufficiently reduce the warpage of printed circuit boards, especially multilayer non-core substrates, and further improvements are desired.

That is, the object of the present invention is to provide a prepreg, a laminate, a metal-clad laminate, a printed circuit board, and a multilayer printed circuit board, which does not have a clear glass transition temperature (Tg) (i.e., no Tg), and can achieve a sufficient reduction in warpage of printed circuit boards, especially multilayer coreless substrates (achieving low warpage).

The inventors of this case worked hard to solve the above-mentioned problems. As a result of research, it was found that the warpage behavior of printed circuit boards used in conventional semiconductor plastic packages has a greater thermal storage elastic modulus in the hardened material of the prepreg. Resin compositions having a high modulus of elasticity and higher are effective, but they are not necessarily limited to this. Furthermore, as a result of diligent research by the inventors of the present case, it was found that among the physical property parameters related to specific mechanical properties in the hardened material obtained by thermally hardening the prepreg, the number of the physical property parameters meets a predetermined condition range. , You can solve the above problems. That is, it was found that the thermal storage elastic modulus and loss elastic modulus of a hardened material obtained by thermally hardening a prepreg conform to a specific range of conditions, and the above problems can be solved, and the present invention has been completed.

That is, the present invention is as follows. [1] A prepreg containing a thermosetting resin, a filler, and a substrate, and a cured product obtained by thermally curing the prepreg at 230 ° C and 100 minutes conforms to the following formulae (1) to (5) ) The range of the physical property parameters about mechanical characteristics: E '(200 ℃) / E' (30 ℃) ≦ 0.90 ... (1) E '(260 ℃) / E' (30 ℃) ≦ 0.85 ... ( 2) E '(330 ℃) / E' (30 ℃) ≦ 0.80… (3) E''max / E '(30 ℃) ≦ 3.0%… (4) E''min / E' (30 ℃) ≧ 0.5% ... (5) In each formula, E 'represents the storage elastic modulus of the hardened product at the temperature shown in parentheses, and E''max represents the loss elastic modulus of the hardened product at a temperature range of 30 ° C to 330 ° C. The maximum value 値, E ″ min represents the minimum value of the loss modulus of the hardened material in the temperature range of 30 ° C to 330 ° C.

[2] The prepreg as in [1], which is more in line with the mechanical characteristics represented by the following formula (6A): E '(30 ° C) ≦ 30GPa ... (6A) In the formula, E' represents the hardened object in the brackets. The storage elastic modulus showing the temperature.

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

[4] The prepreg according to [3], wherein the glass substrate is selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. The fiber composition of one or more glasses in the group.

[5] A laminated board comprising at least one prepreg according to any one of [1] to [4].

[6] A metal foil-clad laminate, comprising: at least one prepreg as described in any one of [1] to [4], and one or both sides of the prepreg arranged on the prepreg Metal foil.

[7] A printed circuit board having an insulating layer formed of a prepreg as in any one of [1] to [4], and a conductor layer formed on a surface of the insulating layer.

[8] A multilayer printed circuit board having a plurality of insulating layers and a plurality of conductor layers. The plurality of insulating layers are composed of a first insulating layer and a second insulating layer, and the first insulating layer is formed by laminating at least one piece or more. [1] to [4] The prepreg is formed, and the second insulating layer is formed by laminating at least one sheet in the direction of one side of the first insulating layer as in [1] to [4]. Formation of any one of the prepregs; the plurality of conductor layers are composed of a first conductor layer and a second conductor layer, the first conductor layer is disposed between the insulation layers of the plurality of insulation layers, and the second conductor layer is disposed On the surface of the outermost layer of the plurality of insulating layers. (Effect of the invention)

According to the present invention, it is possible to provide a prepreg, a laminated board, a metal foil-clad laminated board, a printed circuit board, and a multilayer that can sufficiently reduce the warpage of printed circuit boards, especially multilayer non-core substrates (to achieve low warpage). A printed circuit board.

Hereinafter, this embodiment (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. In addition, in this embodiment, "resin solid content" means a component other than a solvent in a resin composition and a filler unless otherwise specified, and "100 parts by mass of a resin solid content" means a component in the resin composition. The total of components other than the solvent and the filler is 100 parts by mass.

[Prepreg] The prepreg according to this embodiment includes a substrate and a resin composition described later after being impregnated or applied to the substrate. The manufacturing method of the prepreg can be carried out according to a conventional method, and there is no particular limitation. For example, after impregnating or coating the resin composition in this embodiment with a substrate, heating it in a dryer at 100 to 200 ° C for 1 to 30 minutes to make it semi-hardened (B-staged), it can be produced. The prepreg of this embodiment.

In addition, the hardened material obtained by thermally curing the prepreg of this embodiment at 230 ° C and 100 minutes conforms to the numerical range of the physical property parameters regarding mechanical characteristics represented by the following formulas (1) to (5), and is preferably In order to comply with the numerical range of physical property parameters related to mechanical characteristics expressed by the following formulas (1A) to (5A).

E '(200 ℃) / E' (30 ℃) ≦ 0.90… (1) E '(260 ℃) / E' (30 ℃) ≦ 0.85… (2) E '(330 ℃) / E' (30 ℃ ) ≦ 0.80… (3) E''max / E '(30 ℃) ≦ 3.0%… (4) E''min / E' (30 ℃) ≧ 0.5%… (5) 0.40 ≦ E '(200 ℃ ) / E '(30 ℃) ≦ 0.90… (1A) 0.40 ≦ E' (260 ℃) / E '(30 ℃) ≦ 0.85… (2A) 0.40 ≦ E' (330 ℃) / E '(30 ℃) ≦ 0.80… (3A) 0.5% ≦ E''max / E '(30 ℃) ≦ 3.0%… (4A) 3.0% ≧ E''min / E' (30 ℃) ≧ 0.5% ... (5A)

Here, in each formula, E ′ represents the storage elastic modulus of the hardened material at the temperature shown in the brackets, and E ″ max represents the maximum loss elastic modulus of the hardened material in the temperature range of 30 ° C to 330 ° C. E "min represents the minimum loss modulus of elasticity of the cured material in the temperature range of 30 ° C to 330 ° C (E" represents the loss elastic modulus of the cured material).

In the past, with regard to the warping behavior of printed circuit boards, it is believed that a cured composition of a prepreg can achieve a large thermal storage modulus of elasticity and a resin composition having a high modulus of elasticity retention, but this is not necessarily the case. , The number of physical property parameters of mechanical properties of the hardened material obtained by thermally hardening the prepreg at 230 ° C and 100 minutes is in the range of the above formulas (1) to (5), and is preferably the formula In the range of (1A) to (5A), the glass transition temperature (Tg) can be sufficiently increased, and the warpage amount of the laminated board, metal foil-clad laminated board, and printed circuit board, especially the multilayer non-core substrate itself can be sufficient. Decrease.

In other words, the number of physical property parameters of mechanical properties of the hardened material obtained by thermally hardening the prepreg at 230 ° C and 100 minutes is in the range of the above formulas (1) to (5), and more preferably Within the range of formulas (1A) to (5A), ideally there is no clear glass transition temperature (no Tg), and the warpage of printed circuit boards (especially multilayered coreless substrates) can be sufficiently reduced (achieving low warpage) song). That is, if the equations (4) and (5) related to the loss elastic modulus are satisfied, and if the equations (4A) and (5A) are preferably satisfied, it can be said that there is no clear glass transition temperature (Tg) (without Tg) as Synonymous, if the hardened product only conforms to the formulae (4) and (5), it is better to conform to the formulae (4A) and (5A) and does not conform to the formulae (1) to (3). ), The loss of elastic modulus itself is small and it is not easy to elongate, but when it is made into a printed circuit board, this elongation difficulty will cause it to be difficult to achieve low warpage. In contrast, if the hardened material not only conforms to the formulae (4) and (5), preferably the formulae (4A) and (5A), but also conforms to the formulae (1) to (5), and preferably the formulae (1A) to (5A), then Since it does not have Tg, it is not easy to stretch and the printed circuit board tends to achieve low warpage.

In addition, the prepreg according to this embodiment preferably conforms to the mechanical characteristics represented by the following formula (6A), and more preferably conforms to the mechanical characteristics represented by the following formula (6) and / or formula (6B).

E '(30 ° C) ≦ 30GPa ... (6A) E' (30 ° C) ≦ 25GPa ... (6) 1GPa ≦ E '(30 ° C) ... (6B) Here, in the formula, E' represents the aforementioned hardened material in brackets The storage modulus of elasticity at the temperature indicated. That is, the prepreg of this embodiment has an E '(30 ° C) of preferably 30 GPa or less, and more preferably 25 GPa or less. The lower limit of E '(30 ° C) is not particularly limited, but it is preferably 1 GPa or more.

The mechanical properties of the hardened material obtained by thermally curing the prepreg at 230 ° C and 100 minutes are in the range of the above formula (6), which can particularly reduce the warpage of the multilayer coreless substrate.

The method for measuring the mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ″) of the hardened material of the prepreg is not particularly limited. For example, it can be measured by the following method. That is, copper foil (3EC-VLP, made by Mitsui Metals Mining Co., Ltd., thickness 12 μm) was placed on the upper and lower surfaces of one prepreg, and laminated molding was performed at a pressure of 30 kgf / cm ² and a temperature of 230 ° C. for 100 minutes ( Thermal hardening) to obtain a copper-clad laminate with a predetermined thickness of the insulating layer. Then, the obtained copper-clad laminate was cut with a dicing saw to a size of 5.0 mm × 20 mm, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the mechanical properties (storage elastic modulus E 'and loss elastic modulus E'') can be measured by the DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481. At this time, an average 値 of n = 3 can also be obtained.

The content of the resin composition (including the filler (H) described later) in the aforementioned prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and more preferably relative to the total amount of the prepreg. It is 40 to 80% by volume. When the content of the resin composition is within the above range, the moldability tends to be better.

The substrate is not particularly limited, and known products used for various printed circuit board materials may be appropriately selected depending on the intended use and performance. The substrate is, for example, a glass substrate, an inorganic substrate other than glass, an organic substrate, and the like. Among them, a glass substrate is particularly preferable from the viewpoints of high rigidity and stability of heating dimensions. Specific examples of the fibers constituting these substrates are not particularly limited, and the glass substrate is, for example, one selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. More than one glass fiber. Examples of the inorganic substrate other than glass include inorganic fibers other than glass such as quartz. Examples of the organic substrate include poly-paraphenylene terephthalamide (KEVLAR (registered trademark), manufactured by DuPont), and copolymerized para-phenylene terephthalamide. Fully aromatic polyfluorene such as copoly- (paraphenlene / 3,4-oxydiphenylene terephthalamide) (Technora (registered trademark), TEIJIN TECHNO PRODUCTS (shares) company) Amine; Polyesters such as 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (Vectran (registered trademark), Kuraray Co., Ltd.), Zxion (registered trademark, manufactured by KB Seiren); polyparaphenylene benzo double Organic fibers such as poly (p-phenylene-2,6-benzobisoxazole) (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide, etc. These substrates can be used alone or in combination. 2 More than that.

The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, cut felts, and surface felts. The weaving method of the weaving cloth is not particularly limited. For example, plain weaving, basket weave, twill weave, etc. are known, and these publicly known laws can be appropriately selected according to the purpose and performance of the purpose. In addition, a glass woven fabric which has been subjected to a fiber opening treatment or a surface treatment with a silane coupling agent can be preferably used. The thickness and quality of the base material are not particularly limited, and generally about 0.01 to 0.3 mm is suitable. In particular, from the viewpoint of strength and water absorption, a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less is preferable, and a glass woven fabric composed of glass fibers of E glass, S glass, and T glass is more preferable.

[Resin composition] The resin composition of this embodiment used in the prepreg is not particularly limited as long as it contains a thermosetting resin and a filler, and for example, a maleimide compound (A ), An allyl-containing compound (B), and an epoxy resin (C) composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit, and the above formulas (1) to (5) are preferably formulas (1A) ~ (5A) The composition of the range of the number of physical parameters related to mechanical properties. Laminates, metal foil-clad laminates, printed circuit boards, and multilayer coreless substrates containing prepregs containing such resin compositions and substrates can be used to reduce warpage caused by heating such as reflow. Volume tendency.

[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, for example: N -Phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bisamidine 4- (4-maleimide Phenoxy) -phenylphosphonium propane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimide Aminephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, maleimide compounds represented by the following formula (7), and maleimide Prepolymers of compounds, or prepolymers of maleimide and amine compounds. Among them, it is selected from the group consisting of bis (4-maleimideiminophenyl) methane, 2,2-bisamidine 4- (4-maleimimidephenoxy) -phenylarsine propane, and bis (3 -Ethyl-5-methyl-4-maleimidephenyl) methane, and at least one of the group consisting of maleimide imine compounds represented by the following formula (7) is preferable, and particularly The maleimide compound represented by (7) is preferred. By containing such a maleimidine imine compound (A), the thermal expansion coefficient of the obtained hardened | cured material is lower, and heat resistance and the glass transition temperature (Tg) tend to be higher.

[Chemical 1]

Here, in formula (7), R ₅ each independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom. In formula (7), n ₁ represents an integer of 1 or more, preferably an integer of 10 or less, and more preferably an integer of 7 or less.

The content of the maleimide compound (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, and more preferably 100 parts by mass of the resin solid content. It is 35 to 50 parts by mass, and more preferably 35 to 45 parts by mass. When the content of the maleimide compound (A) is within the above range, the thermal expansion coefficient of the obtained hardened product is lower, and the heat resistance tends to be better.

[Allyl-containing compound (B)] The allyl-containing compound (B) is not particularly limited as long as it is a compound having one or more allyl groups in the molecule, and may further have an allyl group Reactive functional groups. The reactive functional group other than allyl is not particularly limited, and examples thereof include a cyanate group (cyanate group), a hydroxyl group, an epoxy group, an amine group, an isocyanate group, an epoxy group, and a phosphate group. Among them, at least one selected from the group consisting of a cyanate group (cyanate 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 ester group, and an epoxy group, it has high flexural strength and flexural modulus of elasticity, low dielectric constant, high glass transition temperature (high Tg), low thermal expansion coefficient, and thermal conductivity. Better tendency.

The allyl-containing compound (B) may be used singly or in combination of two or more kinds. When two or more types of allyl-containing compounds (B) having a reactive functional group other than allyl are used in combination, the reactive functional groups other than allyl may be the same or different. Among them, the allyl-containing compound (B) preferably contains an allyl-containing compound whose reactive functional group is a cyanate group and an allyl-containing compound whose reactive functional group is an epoxy group. When such an allyl-containing compound (B) is used in combination, the bending strength, the bending elastic modulus, the glass transition temperature (Tg), and the thermal conductivity tend to be better.

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

The allyl-containing compound (B) is preferably an allylphenol derivative (D) to be described later and / or an alkenyl-substituted nadicarium imine compound (E). By using such an allyl-containing compound (B), the glass transition temperature (Tg), the thermal expansion coefficient, and the thermal conductivity tend to be better.

The content of the allyl-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, more preferably 100 parts by mass of the resin solid content. It is 25 to 40 parts by mass. When the content of the allyl-containing compound (B) is within the above range, the obtained cured product has softness, flexural strength, flexural modulus of elasticity, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and copper. The foil peeling strength tends to increase.

(Allylphenol Derivative (D)) As far as the allylphenol derivative (D) is concerned, any compound and its derivative in which an allyl group and a phenolic hydroxyl group are directly bonded to the aromatic ring may be used. Specifically, for example, a hydrogen atom of an aromatic ring is replaced with a bisphenol of an allyl group, a hydrogen atom of an aromatic ring is replaced by an allyl group, and a phenolic hydroxyl group is reacted by a reaction other than the hydroxyl group in a reactive functional group other than the allyl group. The modified bisphenol compound modified with a functional group is more specifically a compound represented by the following formula (8), and more specifically, diallyl bisphenol A, diallyl bisphenol A cyanate ester compound, diallyl bisphenol A type epoxy resin.

[Chemical 2]

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

The compound represented by the formula (8) is not particularly limited, for example, 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), the bending strength, the bending elastic modulus, the glass transition temperature (Tg), the thermal expansion coefficient, the thermal conductivity, and the copper foil peeling strength tend to be more improved.

[Chemical 3]

[Chemical 4]

The above bisphenols are not particularly limited, for example: bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bis Phenol M, Bisphenol S, Bisphenol P, Bisphenol PH, Bisphenol TMC, Bisphenol Z. Among them, bisphenol A is preferred.

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. The allyl group number in the molecule of allylphenol derivative (D) is within the above range, and the bending strength, bending elastic modulus, copper foil peeling strength, and glass transition temperature (Tg) are further improved, and the coefficient of thermal expansion is improved. It tends to be low and excellent in thermal conductivity.

The number of reactive functional groups other than allyl in one molecule of the allylphenol derivative (D) is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2. The number of reactive functional groups other than allyl in 1 molecule of the allylphenol derivative (D) is within the above range, and further includes flexural strength, flexural modulus of elasticity, copper foil peeling strength, and glass transition temperature (Tg). Improved, tends to have a low thermal expansion coefficient and excellent thermal conductivity.

The desirable range of the content of the allylphenol derivative (D) is based on the content of the allyl-containing compound (B).

(Nadiqimide compound (E) substituted with alkenyl group) As long as there is at least one aldiyl group substituted nadic acid compound in the molecule, The base compound is not particularly limited. Among them, a compound represented by the following formula (9) is preferable. By using such an alkenyl-substituted nadicarium imine compound (E), the obtained hardened material tends to have a lower thermal expansion coefficient and higher heat resistance.

[Chemical 5]

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

[Chemical 6]

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

[Chemical 7]

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

Moreover, it is more preferable that the aldiyl substituted nadicarium imine compound (E) is a compound represented by the following formula (12) and / or (13). By using such an alkenyl-substituted nadicarium imine compound (E), the hardened product obtained has a lower thermal expansion rate and a higher heat resistance.

[Chemical 8]

[Chemical 9]

The aldiyl substituted nadicarium imine compound (E) can also use a commercial item. Commercial products are not particularly limited, for example: BANI-M (made by Maruzen Petrochemical Co., Ltd., compound represented by formula (12)), BANI-X (made by Maruzen Petrochemical Co., Ltd., compound represented by formula (13)) Wait. These can be used singly or in combination of two or more.

The content of the aldiyl-substituted nadicarium imine compound (E) is preferably 20 to 50 parts by mass, and more preferably 20 to 35 parts by mass relative to 100 parts by mass of the resin solid content. In addition, the total content of the allylphenol derivative (D) and the alkenyl-substituted nadikolide imine compound (E) is preferably 20 to 50 parts by mass, more preferably 35 to 100 parts by mass of the resin solid content. 45 parts by mass. When the content of the aldiyl-substituted nadicarium imine compound (E) is within the above range, the hardened material to be obtained tends to have a lower thermal expansion rate and better heat resistance.

[Epoxy resin (C) composed of bisphenol A-type structural unit and hydrocarbon-based structural unit] As long as there is one epoxy resin (C) composed of bisphenol A-type structural unit and hydrocarbon-based structural unit The compound of the above bisphenol A-type structural unit and one or more hydrocarbon-based structural units is not particularly limited. Among them, a compound represented by the following formula (14) is preferred. By using such an epoxy resin (C) composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit, the storage elastic modulus E 'of the hardened material obtained upon heating tends to be a suitable one for suppressing warpage. .

[Chemical 10]

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, a chlorine atom, or a bromine atom, and X represents an elongation group. Ethoxyethyl, di (ethoxy) ethyl, tri (ethoxy) ethyl, acryloxypropyl, di (propyleneoxy) propyl, tri (propyleneoxy) propyl, or carbon number 2 ~ 15 Is an alkyl group, and n represents a natural number.

As the epoxy resin (C) composed of the bisphenol A-type structural unit and the hydrocarbon-based structural unit, a commercially available product may be used. Commercial products are not particularly limited, for example: EPICLON EXA-4850-150 (made by DIC (stock), a compound having a structure represented by formula (14)), EPICLON EXA-4816 (made by DIC (stock), in formula (14) Where X is an ethylidene compound) and the like. These can be used singly or in combination of two or more.

The content of the epoxy resin (C) composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit is preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the resin solid content. More preferably, it is 10 to 20 parts by mass. The content of the epoxy resin (C) composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit is within the above-mentioned range, and the storage elastic modulus E 'of the hardened material obtained during heating is suitable for suppressing warpage. Sloppy tendency.

[Cyanate Compound (F)] The resin composition of the present embodiment may further contain a cyanate compound (F). The cyanate compound (F) is not particularly limited as long as it is a cyanate compound other than the allylphenol derivative (D). For example, a naphthol aralkyl cyanate represented by the following formula (15), Novolac-type cyanate ester, biphenylaralkyl-type cyanate ester, bis (3,5-dimethyl 4-cyanooxyphenyl) methane, bis (4-cyanooxybenzene) represented by formula (16) Group) methane, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,3,5-tricyanooxybenzene, 1,3-dicyanooxynaphthalene, 1,4- Dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene, 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3, 6-tricyanoxynaphthalene, 4,4'-dicyanooxybiphenyl, bis (4-cyanoxyphenyl) ether, bis (4-cyanoxyphenyl) sulfide, bis (4-cyano Oxyphenyl) fluorene, and 2,2'-bis (4-cyanooxyphenyl) propane; prepolymers of these cyanates and the like. These cyanate ester compounds (F) may be used individually by 1 type, and may use 2 or more types together.

[Chemical 11]

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

[Chemical 12]

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

Among these, the cyanate compound (F) preferably contains a naphthol aralkyl type cyanate represented by the formula (15), a novolac type cyanate represented by the formula (16), and biphenyl One or more of the group consisting of an aralkyl-based cyanate is preferred, and contains a naphthol-aralkyl-based cyanate represented by the formula (15) and a novolac-based cyanide represented by the formula (16) One or more members of the group consisting of acid esters are more preferred. By using such a cyanate ester compound (F), there is a tendency that a hardened product having better flame retardancy, higher hardenability, and a lower thermal expansion coefficient can be obtained.

The manufacturing method of these cyanate ester compounds (F) is not specifically limited, A well-known method can be used for the synthesis method of a cyanate ester compound. The known method is not particularly limited, for example, a method of reacting a phenolic resin and a cyanogen halide in a passive organic solvent in the presence of a basic compound; forming a salt of the phenolic resin and a basic compound in a solution containing water, and thereafter Method for carrying out 2-phase interfacial reaction between the obtained salt and cyanogen halide.

The phenolic resin used as a raw material of the cyanate-formed phenolic compound (F) is not particularly limited. For example, a naphthol aralkyl resin, a novolac phenol resin, Benzoaralkyl type phenolic resin.

[Chemical 13]

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

The naphthol aralkyl type phenol resin represented by the formula (17) can be obtained by condensing a naphthol aralkyl resin and cyanic acid. The naphthol aralkyl-type phenol resin is not particularly limited. For example, naphthols such as α-naphthol and β-naphthol, and -xylylene glycol, α, α'-dimethoxy-p-xylene, And 1,4-bis (2-hydroxy-2-propyl) benzene and other benzenes. The naphthol aralkyl cyanate can be selected from those obtained by condensing a naphthol aralkyl resin obtained as described above with cyanic acid.

The content of the cyanate ester compound (F) is preferably 0.5 to 45 parts by mass, more preferably 10 to 45 parts by mass, still more preferably 15 to 45 parts by mass, and more preferably 20 to 100 parts by mass of the resin solid content. ~ 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 hardened product tend to be further improved.

[Epoxy Compound (G)] The resin composition of this 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-based structural unit described above. The epoxy compound (G) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule other than the aforementioned epoxy resin (C), for example, bisphenol A type epoxy resin, bisphenol E Epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, cresol novolac epoxy resin, biphenyl Epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, trifunctional phenol epoxy resin, 4-functional phenol epoxy resin, propylene oxide epoxy resin, phenol aralkyl epoxy resin , Biphenylaralkyl epoxy resin, aralkyl novolac epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, polyol epoxy resin, isocyanide The urate ring contains an epoxy resin, or a halide thereof. When the allyl-containing compound (B) contains an epoxy group, the epoxy compound (G) is other than the allyl-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 even more preferably 7.5 to 25 parts by mass based on 100 parts by mass of the resin solid content. When the content of the epoxy compound (G) is within the above range, the softness of the obtained cured product, copper foil peeling strength, chemical resistance, and deslagging resistance tend to be further improved.

[Filling material (H)] The resin composition of this embodiment may further contain a filler (H). The filler (H) is not particularly limited, for example, an inorganic filler and an organic filler. Among them, an inorganic filler is preferred, and an organic filler and an inorganic filler are preferably used together. The inorganic filler is not particularly limited, for example: natural silicon dioxide, fused silicon dioxide, synthetic silicon dioxide, amorphous silicon dioxide, Aerosil, hollow silicon dioxide and other silicon dioxides; silicon compounds such as white carbon; titanium White, zinc oxide, magnesium oxide, zirconia and other metal oxides; boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride and other metal nitrides; metal sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide Heat-treated products (heat-treated aluminum hydroxide to reduce part of the crystal water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate ; Alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M -G20 glass, short glass fiber (including E glass, T glass, D glass, S glass, Q glass and other glass powders), hollow glass, spherical glass, etc. In addition, the organic filler is not particularly limited, for example: styrene-based powder, butadiene-based powder, acrylic-based powder, and other rubber powders; core-shell rubber powders; polysiloxane resin powders; polysiloxane rubber powders; and polysiloxanes. Composite powder and so on. The filler (H) may be used alone or in combination of two or more.

It contains a group selected from the group consisting of inorganic fillers, silicon dioxide, aluminum oxide, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride. At least one of the groups is preferable, and at least one selected from the group consisting of silica, alumina, and boehmite is more preferable. By using such a filler (H), the hardened | cured material obtained will tend to have high rigidity and low warpage.

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

[Silane coupling agent and wetting and dispersing agent] The resin composition of this embodiment may further contain a silane coupling agent and a wetting and dispersing agent. By containing a silane coupling agent and a wetting and dispersing agent, the dispersibility of the filler (H), the resin component, the filler (H), and the adhesive strength of the substrate described later tend to be better.

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, for example: γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ- Aminosilane compounds such as aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; silane-based epoxy compounds; γ-acrylic acid propyltrimethoxysilane; acrylic groups Silane-based compounds; cationic silane-based compounds such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane-based compounds and the like. The silane coupling agent may be used singly or in combination of two or more kinds.

The wetting and dispersing agent is not particularly limited as long as it is a dispersing stabilizer for coating applications, for example, DISPERBYK-110, 111, 118, 180, 161, BYK-W996, W9010, W903, etc., manufactured by BYKChemie Japan.

[Other resins, etc.] The resin composition of this embodiment may further contain an allyl-containing compound (hereinafter referred to as "other allyl-containing compounds") other than the allyl-containing compound (B) as necessary. Based compounds "), phenolic resins, oxetane resins, benzo One or two or more of the group consisting of a compound and a compound having a polymerizable unsaturated group. By containing such other resins, the copper foil peeling strength, bending strength, and bending elastic modulus of the obtained cured product tend to be better.

[Other compounds containing allyl groups] Other compounds containing allyl groups are not particularly limited, for example: chloropropylene, allyl acetate, allyl ether, propylene, triallyl cyanurate, triene isocyanurate Propyl ester, diallyl phthalate, diallyl isophthalate, diallyl maleate, and the like.

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

[Phenolic resin] The phenolic resin may be a phenolic resin having two or more hydroxyl groups in one molecule, and generally known ones can be used, and its type 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 phenol resin, and propylene oxide Ester-type phenolic resin, aralkyl novolac-type phenolic resin, biphenylaralkyl-type phenolic resin, cresol novolac-type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol Resin, anthracene phenolic resin, naphthalene skeleton modified novolac phenolic resin, phenol aralkyl phenolic resin, naphthol aralkyl phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, grease Cyclic phenolic resins, polyhydric alcohol phenolic resins, phosphorus-containing phenolic resins, and hydroxyl-containing silicone resins are not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types. By using such a phenol resin, the obtained cured product tends to be more excellent in adhesiveness and flexibility.

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

[Xetane resin] As the oxetane resin, generally known ones can be used, and the type thereof is not particularly limited. Specific examples include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyl Alkyloxetane such as oxetane, 3-methyl-3-methoxymethyloxetane, 3,3'-bis (trifluoromethyl) perfluorooxane Butane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toa Synthetic), OXT-121 (trade name of East Asia Synthetic) and the like. These oxetane resins can be used singly or in combination of two or more kinds. By using such an oxetane resin, the obtained cured product tends to be more excellent in adhesiveness and flexibility.

The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass, relative to 100 parts by mass of the resin solid content. When the content of the oxetane resin is within the above range, the adhesiveness and flexibility of the obtained cured product tend to be more excellent.

[Benzo Compound] benzo As long as the compound is two or more dihydrobenzo in one molecule A ring compound is sufficient, and generally known products are used, and there is no particular limitation on the kind. Specific examples thereof include bisphenol A benzo BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzo BF-BXZ (trade name manufactured by Konishi Chemical), bisphenol S type benzo BS-BXZ (trade name of Konishi Chemical Co., Ltd.) and the like. Benzo The compounds may be used singly or in combination of two or more. By containing such benzo The compound tends to be more excellent in flame retardancy, heat resistance, low water absorption, and low dielectric properties of the obtained cured product.

Benzo The content of the compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and even more preferably 3 to 80 parts by mass, with respect to 100 parts by mass of the resin solid content. Benzo When the content of the compound is within the above range, the heat resistance of the obtained hardened product tends to be more excellent.

[Compounds Having Polymerizable Unsaturated Group] As for the compounds having polymerizable unsaturated group, generally known ones can be used, and the kind 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, and (meth) 2-hydroxypropyl acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentaerythritol tetra (methyl) (Meth) acrylates, dipentaerythritol hexa (meth) acrylates and other mono- or polyhydric alcohols (meth) acrylates; bisphenol A epoxy (meth) acrylates, bisphenol F epoxy Epoxy (meth) acrylates such as (meth) acrylates; benzocyclobutene resins; (bis) maleimide resins and the like. These unsaturated compounds can be used singly or in combination of two or more kinds. By containing such a polymerizable unsaturated group-containing compound, there is a tendency that the obtained cured product is more excellent in heat resistance and alkali resistance.

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 even more preferably 3 to 80 parts by mass, relative to 100 parts by mass of the resin solid content. When the content of the compound having a polymerizable unsaturated group is within the above-mentioned range, the obtained cured product tends to be more excellent in heat resistance and alkali resistance.

[Hardening Accelerator] The resin composition of this embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, for example: imidazoles such as triphenylimidazole; benzamidine peroxide, laurel oxide, acetamidine peroxide, benzamidine peroxychloride, and diperoxyphthalate Organic peroxides such as tributyl ester; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N -Dimethylpyridine, 2-N-ethylaniline ethanol, tri-n-butylamine, pyridine, quinoline, N-methyl Tertiary amines such as phosphine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; Organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron ethylacetonate; etc. Metal salts dissolved in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; dioctyl tin oxide, other alkyl tin, and alkyl tin oxide Organotin compounds, etc. Among these, triphenylimidazole is particularly preferable because it promotes a hardening reaction and tends to have excellent glass transition temperature (Tg) and thermal expansion coefficient.

[Solvent] The resin composition of this embodiment may further contain a solvent. By containing a solvent, the viscosity at the time of preparation of a resin composition is lowered, the operability is further improved, and the impregnation property with respect to a substrate described later tends to be further improved.

The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition, for example, ketones such as acetone, methyl ethyl ketone, and methylcythrene; aromatic hydrocarbons such as toluene and xylene; Dimethylformamide and other amines; propylene glycol monomethyl ether and its acetate. The solvents may be used singly or in combination of two or more kinds.

[Manufacturing method of resin composition] The manufacturing method of the resin composition of the present embodiment is not particularly limited, and for example, a method in which each component is sequentially mixed with a solvent and sufficiently stirred. In this case, in order to uniformly dissolve or disperse each component, a known treatment such as stirring, mixing, and kneading treatment may be performed. Specifically, the dispersibility of the filler (H) with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading processes can be appropriately implemented using, for example, a device for mixing purposes such as a ball mill and a bead mill, or a known device such as a revolving or self-converting mixing device.

Moreover, when preparing 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 it is a resin that can dissolve the resin. Specific examples are as described above.

[Use] The prepregs in accordance with the formulae (1) to (5) of the present embodiment, and preferably in the range of the number of physical parameters of the mechanical properties represented by the formulae (1A) to (5A), can be ideally used as the insulating layer. , Laminated board, metal-clad laminated board, printed circuit board, or multilayer printed circuit board. Hereinafter, a laminated board, a metal-clad laminated board, and a printed circuit board (including a multilayer printed circuit board) will be described.

[Laminate and Metal-Foil Laminate] The laminate according to this embodiment includes the above-mentioned prepreg in which at least one sheet is laminated. The metal foil-clad laminate according to this embodiment includes the laminate according to this embodiment (that is, at least one sheet of the prepreg according to this embodiment is laminated), and the laminate is disposed on the laminate. Single-sided or double-sided metal foil (conductor layer). By using the pre-impregnation in the range of the number and range of the physical property parameters regarding the mechanical properties (storage elastic modulus and loss elastic modulus) expressed in accordance with the above formulas (1) to (5), preferably formulas (1A) to (5A) The laminated plate and the metal-clad laminated plate according to this embodiment tend to have a clear glass transition temperature (no Tg) and to sufficiently reduce warpage (to achieve low warpage).

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

The method of forming a laminated board, a metal-clad laminated board, and its forming conditions are not particularly limited, and methods and conditions for a general laminated board and multilayer board for a printed circuit board can be used. For example, when forming a laminated board or a metal-clad laminated board, a multi-stage pressing machine, a multi-stage vacuum pressing machine, a continuous forming machine, an autoclave forming machine, etc. can be used. In addition, in the forming (laminating forming) of a laminated plate or a metal-clad laminated plate, generally, the temperature is 100 to 300 ° C., the pressure is 2 to 100 kgf / cm ² , and the heating time is 0.05 to 5 hours. Range. Furthermore, if necessary, post-curing may be performed at a temperature of 150 to 300 ° C. Especially when using a multi-stage press, consider the viewpoint of fully promoting the hardening of the prepreg. The temperature is 200 ° C to 250 ° C, the pressure is 10 to 40kgf / cm ² , and the heating time is 80 minutes to 130 minutes. The temperature is 215 ° C to 235 ° C, A pressure of 25 to 35 kgf / cm ² and a heating time of 90 minutes to 120 minutes are more desirable. Moreover, a multilayer board can also be produced by combining the above-mentioned prepreg and a wiring board for an inner layer which is separately produced, and forming a multilayer board.

[Printed Circuit Board] The printed circuit board of this embodiment has an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer contains the prepreg. For example, by forming a predetermined wiring pattern on the metal foil-clad laminate of the present embodiment described above, it is ideal as a printed circuit board. As described above, the metal foil-clad laminate of the present embodiment does not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieving low warpage). Therefore, it is a printing requiring such performance. The circuit board is particularly effective.

Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the above-mentioned metal-clad laminate (copper-clad laminate, etc.) is prepared. The surface of the metal foil-clad laminate is etched to form an inner-layer circuit, and an inner-layer substrate is produced. The inner layer circuit surface of this inner layer substrate is optionally subjected to a surface treatment to improve the adhesive strength, and then the above-mentioned prepregs of the required number are laminated on the inner layer circuit surface, and then the outer circuit metal is laminated on the outer layer circuit. The foil is heated and pressurized, and is integrally formed (laminated). In this manner, a multilayer laminated board having a base material and an insulating layer made of 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 lamination forming and the forming conditions thereof are the same as those of the above-mentioned laminated plate or metal foil-clad laminated plate. Then, after applying through-hole processing for the through-holes and interlayer holes to this multilayer laminated board, in order to remove the slag, which is a residue from the resin component resin contained in the hardened material layer, a slag removal treatment is performed. After that, a plating metal film is formed on the wall surface of the hole to allow the inner layer circuit and the outer layer metal foil to be conducted, and then the metal foil for the outer layer circuit is etched to form an outer layer circuit to manufacture a printed circuit board.

In this case, for example, the aforementioned prepreg (the substrate and the resin composition adhered to the substrate) constitute an insulating layer.

When a metal foil-clad laminate is not used, a printed circuit board can be formed by forming a conductor layer for a circuit on the prepreg. In this case, the formation of the conductive layer can also be performed by an electroless plating method.

In addition, as shown in FIG. 9, the printed circuit board of this embodiment preferably has a plurality of insulating layers and a plurality of conductor layers, and the plurality of insulating layers are composed of a first insulating layer (1) and a second insulating layer (2). The first insulating layer (1) is formed by laminating at least one piece of the above-mentioned prepreg, and the second insulating layer (2) is oriented on a single side of the first insulating layer (1) (the lower direction in the figure). ) Is formed by laminating at least one or more of the above prepregs; the plurality of conductor layers are composed of a first conductor layer (3) and a second conductor layer (3), and the first conductor layer (3) is arranged there Between the insulating layers of the plurality of insulating layers (1,2), the second conductor layer (3) is disposed at the outermost layer of the plurality of insulating layers (1,2). According to the knowledge and knowledge of the inventors of this case, a general laminated board is formed by laminating other prepregs on both sides of a core substrate, that is, a prepreg, to form a multilayer printed circuit board. The prepreg is a coreless multilayer produced by laminating another prepreg in which the second insulating layer (2) is laminated on only one side of the prepreg forming one of the first insulating layers (1). Printed circuit boards (multilayer coreless substrates) are particularly effective.

In other words, when the prepreg and the resin composition of this embodiment are used in a printed circuit board, the amount of warpage can be effectively reduced. Although there is no particular limitation, a multilayered coreless substrate is particularly effective in the printed circuit board. That is, the general printed circuit board generally adopts a symmetrical structure on both sides, which tends to be difficult to warp, and the multilayer non-core substrate is prone to become asymmetrical on both sides. Therefore, it is more likely to warp than a normal printed circuit board Propensity. Therefore, by using the prepreg and the resin composition of this embodiment, it is possible to particularly effectively reduce the warpage amount of the multilayer coreless substrate that has tended to warp in the past.

9 shows a structure in which two pieces of the second insulating layer (2) are laminated on one piece of the first insulating layer (1) (that is, a structure in which most of the insulating layers are three layers), but the second insulating layer (2 ) May be 1 piece or 2 or more pieces. Therefore, the first conductor layer (3) may be one layer or two or more layers.

As above, the prepregs related to the number of physical parameters of the mechanical properties (storage elastic modulus and loss elastic modulus) expressed by the formulas (1A) to (5A) are preferably the formulas (1A) to (5A). In the printed circuit board of the present embodiment having the above-mentioned structure, especially the multilayer non-core substrate, the clear glass transition temperature (without Tg) does not exist and the warpage is sufficiently reduced (achieving low warpage), so it can be particularly effective Used as printed circuit boards for semiconductor packages and multilayer coreless substrates. [Example]

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

[Synthesis Example 1] In a synthesis reactor for an α-naphthol aralkyl cyanate compound (SN495VCN), an α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Nissin Made by ferrochemical (stock): those containing naphthol aralkyl repeating unit number n is 1 to 5.) 0.47 moles (in terms of OH group) are dissolved in 500 ml of chloroform, and 0.7 mole of triethylamine is added to this solution. . Keeping the temperature at -10 ° C, it took 1.5 hours to add 300 g of a 0.93 mole of cyanogen chloride in chloroform solution to the reactor, and stirred for 30 minutes after the dropwise addition. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise to the reactor, and the mixture was stirred for 30 minutes to complete the reaction. After the by-product triethylamine hydrochloride was separated and filtered from the reaction solution, the obtained filtrate was washed with 500 ml of 0.1 N hydrochloric acid, and then repeatedly washed with 500 ml of water 4 times. This was dried over sodium sulfate, evaporated at 75 ° C, and degassed at 90 ° C under reduced pressure to obtain an α-naphthol aralkyl cyanate compound represented by the formula (15) above (R in the formula ⁶ are all hydrogen atoms.). The obtained α-naphthol aralkyl cyanate compound was analyzed by infrared absorption spectrum, and it was confirmed that there was absorption of a cyanate group near 2264 cm ^-1 .

[Example 1] 45 parts by mass of a maleimide compound (A) (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide imine equivalent 186 g / eq.), And an allyl-containing compound ( B) 34 parts by mass of an alkenyl-substituted nadicarium imine compound (E) (BANI-M, manufactured by Maruzan Petrochemical Co., Ltd., allyl equivalent: 286 g / eq.), And composed of a bisphenol A type structure 10 parts by mass of epoxy resin (C) (EPICLONEXA-4850-150, manufactured by DIC Corporation, epoxy equivalent: 450 g / eq.) Composed of a unit and a hydrocarbon-based structural unit, Synthesis Example 1 of a cyanate compound (F) 1 part by mass of α-naphthol aralkyl cyanate compound (SN495VCN, cyanate equivalent: 261 g / eq.), Epoxy compound (G) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd.), Oxygen equivalent: 320 g / eq.) 10 parts by mass, 120 parts by mass of silicon dioxide slurry (SC-2050MB, manufactured by Admatechs), and polysilicone composite powder (KMP-600, Shin-Etsu) 20 parts by mass of Chemical Industry Co., Ltd., 5 parts by mass of Silane Coupling Agent (Z-6040, manufactured by Toray Dow Corning Co., Ltd.), 1 part by mass of Wetting Dispersant (manufactured by DISPERBYK-161, BYKChemie Japan Co., Ltd.), And triphenylimidazole (Wako Pure Chemical Industries, Ltd.) Parts) Ltd.) and 0.5 mass mixed with 0.1 parts by mass of zinc octylate (Nihon Kagaku Sangyo (shares), Ltd.), diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on E glass woven cloth (IPC # 2116, manufactured by Arisawa Manufacturing 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 fabric (manufactured by Unitika (IPC), IPC # 1030), and dried by heating at 160 ° C for 3 minutes to obtain a resin composition content of 73% by volume. Prepreg.

[Example 3] 43 parts by mass of a maleimide imine compound (A) (BMI-2300), an allyl-containing compound (B), and an alkenyl-substituted nadic acid imide compound (E) (BANI -M) 32 parts by mass, and 10 parts by mass of epoxy resin (C) (EPICLONEXA-4816, manufactured by DIC (stock), epoxy equivalent: 403 g / eq.) Composed of bisphenol A-type structural unit and hydrocarbon-based structural unit. 5. 5 parts by mass of the α-naphthol aralkyl cyanate compound (SN495VCN) of Synthesis Example 1 of the cyanate compound (F), epoxy compound (G) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd.), Epoxy equivalent: 320 g / eq.) 10 parts by mass, 100 parts by mass of silica dioxide (SC-2050MB) as filler (H), 100 parts by volume of the same silica (SC-5050MOB, manufactured by Admatechs) 20 parts by mass of the same polysiloxane composite powder (KMP-600), 5 parts by mass of the silane coupling agent (Z-6040), and 2 parts by mass of the wetting and dispersing agent (DISPERBYK-111, manufactured by BYKChemie Japan) It was mixed with 1 part by mass of (DISPERBYK-161) and 0.5 part by mass of triphenylimidazole as a hardening accelerator and 0.1 part by mass of zinc octoate, and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric (IPC # 2116), followed by heating and drying 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 on an E glass woven fabric (IPC # 1030), followed by heating and drying at 160 ° C for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Comparative Example 1] 51 parts by mass of a maleimidine imine compound (A) (BMI-2300), an allyl-containing compound (B), and an alkenyl-substituted nadic acid imide compound (E) (BANI -M) 38 parts by mass, 1 part by mass of α-naphthol aralkyl cyanate compound (SN495VCN) in Synthesis Example 1 and 10 parts by mass of epoxy compound (G) (NC-3000FH) Parts, 120 parts by mass of silicon dioxide slurry (SC-2050MB) as filler (H), 20 parts by mass of polysiloxane compound powder (KMP-600), and 5 parts by mass of silane coupling agent (Z-6040) 1, 1 part by mass of a wet dispersant (DISPERBYK-161), and 0.5 part by mass of triphenylimidazole as a hardening accelerator and 0.1 part by mass of zinc octoate, and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric (IPC # 2116), followed by heating and drying 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 on an E glass woven fabric (IPC # 1030), followed by heating and drying at 160 ° C for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Comparative Example 3] 49 parts by mass of a maleimidine imine compound (A) (BMI-2300), an allyl-containing compound (B), and an alkenyl-substituted nadic acid imide compound (E) (BANI -M) 36 parts by mass, 5 parts by mass of α-naphthol aralkyl type cyanate compound (SN495VCN) of Synthesis Example 1 of cyanate compound (F), and 10 parts by mass of epoxy compound (G) (NC-3000FH) Parts, 100 parts by mass of silicon dioxide slurry (SC-2050MB) as the filler (H), 100 parts by mass of the same silicon dioxide slurry (SC-5050MOB), and 20 parts by mass of the polysiloxane compound powder (KMP-600) Parts, 5 parts by mass of silane coupling agent (Z-6040), 2 parts by mass of wet dispersant (DISPERBYK-111) and 1 part by mass of (DISPERBYK-161), and 0.5 parts by mass of triphenylimidazole as a hardening accelerator And mixed with 0.1 part by mass of zinc octoate, and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric (IPC # 2116), followed by heating and drying 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), followed by heating and drying 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 KI Kasei Co., Ltd., maleimide equivalent: 221 g / eq.), Synthesis Example 1 of a cyanate compound (F) 35 parts by mass of α-naphthol aralkyl cyanate compound (SN495VCN), 50 parts by mass of epoxy compound (G) (NC-3000FH), and silicon dioxide slurry (SC-2050MB) as filler (H) ) 100 parts by mass, 100 parts by mass of the same silica slurry (SC-5050MOB) and 20 parts by mass of the same polysiloxane compound powder (KMP-600), 5 parts by mass of the silane coupling agent (Z-6040), and a wetting and dispersing agent 2 parts by mass of (DISPERBYK-111) and 1 part by mass of (DISPERBYK-161), and 0.5 parts by mass of triphenylimidazole as a hardening accelerator and 0.1 part by mass of zinc octoate, and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric (IPC # 2116), followed by heating and drying 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 on an E glass woven fabric (IPC # 1030), followed by heating and drying at 160 ° C for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume.

[Physical property measurement evaluation] Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, a sample for physical property measurement evaluation was prepared according to the procedures shown in the following items, and the mechanical properties (storage elastic modulus, storage elastic modulus, And loss modulus of elasticity), physical property parameters related to mechanical properties in formulas (1) to (5) and formulas (1A) to (5A), glass transition temperature (Tg), warpage amount (2 types), and reflow The shrinkage of the substrate before and after the step. The results of the examples are summarized in Table 1, and the results of the comparative examples are summarized in Table 2.

[Mechanical characteristics] Copper foil (3EC-VLP, Mitsui Metals Mining Co., Ltd., thickness 12 μm) was placed on the upper and lower sides of one sheet of prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 6, under a pressure of 30 kgf / Lamination (thermal curing) was performed for 100 minutes under conditions of cm ² and a temperature of 230 ° C. to obtain a copper-clad laminated board having a predetermined insulating layer thickness. The obtained copper-clad laminate was cut with a dicing saw to a size of 5.0 mm × 20 mm, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the mechanical properties (storage elastic modulus E 'and loss elastic modulus E'') were measured by a dynamic viscoelasticity analyzer (manufactured by TAINSTRUMENT) in accordance with JIS C6481 according to DMA method (average of n = 3) .

[Glass transition temperature (Tg)] Copper foils (3EC-VLP, made by Mitsui Metals Mining Co., Ltd., thickness 12 μm) are arranged on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 6, Lamination molding (thermal curing) was performed for 100 minutes under conditions of a pressure of 30 kgf / cm ² and a temperature of 230 ° C. to obtain a copper-clad laminated board having a predetermined insulating layer thickness. The obtained copper-clad laminate was cut with a dicing saw to a size of 12.7 mm × 2.5 mm, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the glass transition temperature (Tg) (n = 3 average 値) was measured by a DMA method using a dynamic viscoelasticity analyzer (manufactured by TAINSTRUMENT) in accordance with JISC 6481.

[Warpage: Bimetal method] First, copper foils (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd.) were placed on the upper and lower sides of one of the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and the thickness 12 μm), lamination (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-clad laminate. The copper foil was then removed from the obtained copper-clad laminate. Next, one sheet of the prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 6 was further arranged on one side of the laminated board from which copper foil was removed, and the above-mentioned copper foil (3EC-VLP, Mitsui The thickness is 12 μm, made by Metal Mining Co., Ltd., and laminated molding (thermosetting) was performed for 120 minutes under a condition of a pressure of 30 kgf / cm ² and a temperature of 220 ° C. to obtain a copper-clad laminate. Furthermore, the copper foil was removed from the obtained copper-clad laminated sheet to obtain a laminated sheet. Then, a strip-shaped 20 mm × 200 mm plate was cut out from the obtained laminated plate, and the surface of the second prepreg was laminated upward, and the maximum amount of warpage at both ends in the longitudinal direction was measured with a metal ruler.値, this average 値 is defined as the "warpage amount" measured by the bimetal method.

[Warpage: Multi-layer coreless substrate] First, as shown in FIG. 1, ultra-thin copper foil (b1) (MT18Ex, Mitsui Metals Mining Co., Ltd.) with a carrier will be attached to both sides of the prepreg that becomes the support (a). ), The thickness of the carrier copper foil is 5), and the copper foil surface is arranged facing the prepreg side, and the prepregs (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 are further disposed thereon, and copper is further disposed thereon. Foil (d) (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd., thickness 12 μm), laminated for 120 minutes at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. to obtain a copper-clad foil as shown in FIG. 2 Laminated boards.

Next, the copper foil (d) of the obtained copper-clad laminate shown in FIG. 2 is etched into a predetermined wiring pattern as shown in FIG. 3 to form a conductor layer (d ′). Then, the prepregs (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 are arranged on the laminated board shown in FIG. 3 where the conductive layer (d ') has been formed, as shown in FIG. 4, An ultra-thin copper foil (b2) with a carrier (MT18Ex, manufactured by Mitsui Metals Mining Co., Ltd., 5 μm thick) was further disposed thereon, and laminated for 120 minutes under a condition of a pressure of 30 kgf / cm ² and a temperature of 230 ° C. A copper-clad laminate shown in FIG. 5 was obtained.

Next, in the copper-clad laminate shown in FIG. 5, the carrier copper foil and the electrode of the ultra-thin copper foil (b1) with a carrier arrange | positioned on the support body (a) (prepreg for hardened support body) are arrange | positioned. The thin copper foil was peeled to peel off the two laminates from the support (a) as shown in FIG. 6, and the carrier was further removed from the ultra-thin copper foil (b2) with a carrier in the upper part of each of these laminates. The copper foil was peeled. Then, the obtained ultra-thin copper foils on each of the obtained laminates were processed by a laser processing machine, and as shown in FIG. 7, predetermined through holes (v) were formed by electroless copper plating. Then, for example, as shown in FIG. 8, a predetermined wiring pattern is etched to form a conductor layer to obtain a multilayer coreless panel (size: 500 mm × 400 mm). Then, the total amount of warpage at the four corners of the panel and the center of the four sides was measured with a metal ruler, and the average value was defined as the "warpage" of the multi-layer, non-core substrate panel.

[Substrate shrinkage ratio before and after the reflow step] Copper foil (3EC-VLP, made by Mitsui Metals Mining Co., Ltd., thickness 12 μm) was placed on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 6, Lamination was performed under conditions of a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a copper-clad laminate. Then, the obtained copper-clad laminate was uniformly drilled at 9 o'clock in a grid pattern using a drill, and then the copper foil was removed.

Then, first, the distance (distance I) between the holes of the laminated plate from which the copper foil was removed was measured. Then, this laminated board was subjected to a reflow treatment using a SALAMANDER reflow device at a maximum temperature of 260 ° C. After that, the distance (distance II) between the holes in the laminated plate was measured again. Then, the measured distance I and distance II are substituted into the following formula (I), and the dimensional change rate of the substrate subjected to the reflow process is determined. This is defined as the shrinkage rate of the substrate before and after the reflow step. ((Distance I)-(distance II)) / distance I × 100 ... Formula (I)

【Table 1】

【Table 2】 [Industrial availability]

The prepreg of this embodiment has industrial applicability as a material for a laminated board, a metal-clad laminated board, a printed circuit board, or a multilayer printed circuit board. In addition, this application is based on Japanese Patent Application No. 2016-255270 filed on December 28, 2016, and the contents thereof are incorporated herein.

1‧‧‧The first insulation layer

2‧‧‧ 2nd insulating layer

3‧‧‧conductor layer

a‧‧‧ support

b1‧‧‧ ultra-thin copper foil

b2‧‧‧thin copper foil

c1‧‧‧prepreg

c2‧‧‧prepreg

d‧‧‧copper foil

d’ ‧‧‧conductor layer

V‧‧‧through hole

FIG. 1 shows a processing flowchart of an example of a procedure for manufacturing a multi-layer coreless substrate panel (however, the manufacturing method of a multi-layer coreless substrate is not limited to this. The same is shown in FIGS. 2 to 8 below). FIG. 2 shows a processing flowchart of an example of a process for manufacturing a multi-layer panel without a core substrate. FIG. 3 shows a processing flowchart of an example of a procedure for manufacturing a multi-layer coreless panel. FIG. 4 shows a processing flowchart of an example of a procedure for manufacturing a multi-layered coreless panel. FIG. 5 shows a processing flowchart of an example of a process for manufacturing a multi-layer panel without a core substrate. FIG. 6 shows a processing flowchart of an example of a procedure for manufacturing a multi-layered coreless panel. FIG. 7 shows a processing flowchart of an example of a process for manufacturing a multi-layer panel without a core substrate. FIG. 8 shows a processing flowchart of an example of a procedure for manufacturing a multi-layer coreless panel. FIG. 9 is a partial cross-sectional view showing the structure of an example of a multi-layer coreless panel.

Claims (8)

A prepreg containing a thermosetting resin, a filler, and a base material, and a cured product obtained by thermally curing the prepreg at 230 ° C and 100 minutes conforms to the following formulae (1) to (5) The range of the physical parameter about mechanical properties: E '(200 ℃) / E' (30 ℃) ≦ 0.90… (1) E '(260 ℃) / E' (30 ℃) ≦ 0.85… (2) E '(330 ℃) / E' (30 ℃) ≦ 0.80… (3) E''max / E '(30 ℃) ≦ 3.0% ... (4) E''min / E' (30 ℃) ≧ 0.5% … (5) In each formula, E ′ represents the storage elastic modulus of the hardened product at the temperature indicated in parentheses, and E ″ max represents the maximum loss of the elastic modulus of the hardened product in the temperature range of 30 ° C to 330 ° C.値, E ″ min represents the minimum loss modulus of the hardened material in the temperature range of 30 ° C to 330 ° C 値. For example, the prepreg of item 1 of the patent application scope is more in line with the mechanical characteristics represented by the following formula (6A): E '(30 ℃) ≦ 30GPa ... (6A) where E' represents the hardened material in the brackets. The storage elastic modulus showing the temperature. For example, the prepreg according to item 1 or 2 of the patent application scope, wherein the substrate is a glass substrate. For example, the prepreg according to item 3 of the patent application scope, wherein the glass substrate is selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. The fiber composition of one or more glasses in the group. A laminated board having at least one or more prepregs according to any one of claims 1 to 4 of the scope of patent application. A metal foil-clad laminated board comprising: at least one or more prepregs according to any one of claims 1 to 4 of the scope of patent application, and metal arranged on one or both sides of the prepreg Foil. A printed circuit board includes an insulating layer formed of a prepreg as in any one of claims 1 to 4, and a conductor layer formed on a surface of the insulating layer. A multi-layer printed circuit board having a plurality of insulating layers and a plurality of conductor layers. The plurality of insulating layers are composed of a first insulating layer and a second insulating layer. The prepreg of any one of items 1 to 4, the second insulating layer is formed by laminating at least one piece in the direction of one side of the first insulating layer. One of the prepregs is formed; the plurality of conductor layers are composed of a first conductor layer and a second conductor layer, the first conductor layer is disposed between each of the plurality of insulation layers, and the second conductor layer is disposed between The outermost surface of the plurality of insulating layers.