WO2016088744A1

WO2016088744A1 - Resin sheet and printed wiring board

Info

Publication number: WO2016088744A1
Application number: PCT/JP2015/083715
Authority: WO
Inventors: 秀和出井; 誠司四家; 恵一長谷部
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2014-12-01
Filing date: 2015-12-01
Publication date: 2016-06-09
Also published as: JPWO2016088744A1; JP6638887B2; TWI680867B; TW201636211A

Abstract

The purpose is to provide a resin sheet serviceable as an insulating layer in a printed wiring board material, the resin sheet including a resin composition which, when made into a resin sheet, has excellent ease of handling, as well as affording excellent cohesion between the insulating layer and a conducting layer formed by plating the surface thereof. This resin sheet includes an outer layer of any one material selected from the group consisting of polymer films, metal foils, and metal films, and an insulating layer laminated onto the outer layer, wherein the insulating layer contains an epoxy compound (A), a cyanic acid ester compound (B), an inorganic filler (C), a first acrylonitrile-butadiene rubber (D) having a weight-average molecular weight, measured by GPC, of 100,000 or greater, and a second acrylonitrile-butadiene rubber (E) having a weight-average molecular weight of 1,000-30,000.

Description

Resin sheet and printed wiring board

The present invention relates to a resin sheet and a printed wiring board useful as a material for an insulating layer of a printed wiring board.

In recent years, electronic devices are becoming smaller and higher performance. In multilayer printed wiring boards, in order to improve the mounting density of electronic components, miniaturization of conductor wiring is progressing, and the wiring forming technology is desired. As a method of forming high-density fine wiring on the insulating layer, an additive method in which a conductor layer is formed only by electroless plating, or a conductor layer is formed by electrolytic plating after forming a thin copper layer on the entire surface by electroless plating. Then, a semi-additive method for flash-etching a thin copper layer after that is known.

It is desirable to reduce the roughness of the surface of the insulating layer as much as possible because the plating in the deep part of the physical anchor cannot be removed in the flash etching process in the subsequent process. On the other hand, since the roughness of the surface of the insulating layer is small, the adhesion strength between the conductor layer and the insulating layer tends to decrease. Therefore, there is a demand for an insulating layer resin composition having a high interface adhesion strength with a conductor layer even when the roughness of the insulating layer surface is small.

In addition, due to the miniaturization and high density of multilayer printed wiring boards, studies are being actively conducted to reduce the thickness of laminated boards used in multilayer printed wiring boards. As the multilayer printed wiring board becomes thinner, the insulating layer is also required to be thinner, and a resin sheet that does not contain glass cloth and has good handling properties is required. Along with the reduction in thickness, problems such as a decrease in mounting reliability and an increase in warpage of the multilayer printed wiring board arise, so that the resin composition used as the material for the insulating layer is also required to have high adhesion and a high glass transition temperature. .

In response to this, various efforts have been made. For example, Patent Document 1 discloses a technique of adding liquid rubber for improving crack resistance from the viewpoint of improving handling properties. Specifically, the document includes (A) a ring structure-containing polymer resin that is a hydrogenated product of a ring-opening polymer of a norbornene monomer having at least one functional group of an acid anhydride group and a carboxyl group, and (B) curing. A resin composition containing an epoxy compound as an agent, (C) an imidazole compound having a ring structure-containing substituent, and (D) a liquid rubber that is liquid polybutadiene is disclosed.

Patent Document 2 discloses a technique using a rubber component for the purpose of improving adhesiveness. The rubber component may be solid or liquid at room temperature (25 ° C.), but it is described that it is preferably liquid from the viewpoint of improving fluidity.

Patent Document 3 discloses that a cured product of a curable resin composition containing a mixture of a cyanate ester resin composition and an acrylonitrile-butadiene copolymer or a pre-reacted product has excellent flexibility and good elasticity. Is described.

Japanese Patent No. 4277440 International Publication No. 2013/042724 Pamphlet JP-A-56-157424

However, the method described in Patent Document 1 can improve crack resistance, but does not describe any concept of high glass transition temperature.

Further, although the method described in Patent Document 2 is excellent in adhesiveness and fluidity, the document does not describe the flexibility of the semi-cured resin sheet at all.

Furthermore, Patent Document 3 describes that the resin sheet obtained from the resin composition has excellent flexibility and elasticity, but does not describe any flexibility of the semi-cured resin sheet. Moreover, the concept of the adhesiveness of the conductor layer formed by plating and the resin layer is not described at all.

The present invention has been made in view of the problems described above, and its purpose is to provide an excellent handling property when used as an insulating layer in a printed wiring board material, and an insulating layer and a conductor layer formed on the surface thereof by plating. It is providing the resin sheet which is excellent in adhesiveness, and has a high glass transition temperature when fully cured, and a printed wiring board using the resin sheet.

As a result of earnest studies, the present inventors have selected a resin sheet comprising an outer layer that is one type selected from the group consisting of a polymer film, a metal foil, and a metal film, and an insulating layer laminated on the outer layer. The insulating layer is an epoxy compound (A), a cyanate ester compound (B), an inorganic filler (C), and a first acrylonitrile-butadiene rubber having a weight average molecular weight measured by GPC of 100,000 or more. It has been found that the above problems can be solved by (D) and a resin sheet containing acrylonitrile-butadiene rubber (E) having a weight average molecular weight of 1,000 to 30,000, and the present invention has been achieved.
[1] A resin sheet comprising an outer layer that is any one selected from the group consisting of a polymer film, a metal foil, and a metal film, and an insulating layer laminated on the outer layer,
The insulating layer is an epoxy compound (A), a cyanate ester compound (B), an inorganic filler (C), and a first acrylonitrile-butadiene rubber (D) having a weight average molecular weight measured by GPC of 100,000 or more. And a second acrylonitrile-butadiene rubber (E) having a weight average molecular weight of 1,000 to 30,000.
[2] The resin sheet according to [1], wherein the content X of the first acrylonitrile-butadiene rubber (D) is 0 <X <15 parts by mass with respect to 100 parts by mass of the resin solid content.
[3] The resin according to [1] or [2], wherein the content Y of the second acrylonitrile-butadiene rubber (E) is 0 <Y <15 parts by mass with respect to 100 parts by mass of the resin solid content. Sheet.
[4] The sum X + Y of the content X of the first acrylonitrile-butadiene rubber (D) and the content Y of the second acrylonitrile-butadiene rubber (E) is 0 < The resin sheet according to any one of [1] to [3], wherein X + Y <15 parts by mass.
[5] The resin sheet according to any one of [1] to [4], wherein the insulating layer further contains a maleimide compound (F).
[6] The resin sheet according to any one of [1] to [5], wherein the polymer film is any one selected from the group consisting of polyester, polyimide, and polyamide.
[7] The insulating layer is obtained by applying a resin composition containing the components (A) to (E) on the outer layer, and then drying and solidifying by heating or reduced pressure. [1 ]-The resin sheet as described in any one of [6].
[8] A printed wiring comprising the insulating layer according to any one of [1] to [7], which is laminated on a circuit board having a core substrate and a conductor circuit formed on the core substrate. Board.
[9] The printed wiring board according to [8], wherein the insulating layer is surface-treated and includes a conductor layer patterned on the surface.
[10] The printed wiring board according to [9], wherein the surface treatment is a desmear treatment including a roughening treatment with a swelling agent and an alkaline oxidizing agent, and a neutralization treatment with an acidic reducing agent.
[11] The printed wiring board according to [9] or [10], wherein the conductor layer includes a conductor layer formed by a semi-additive method or a conductor layer formed by a subtractive method.
[12] The printed wiring board according to [9] or [10], wherein the conductor layer includes a conductor layer obtained by etching an outer layer made of the metal foil or metal film according to [1].

The resin sheet of the present invention exhibits at least one, preferably all of the following effects (1) to (4).
(1) The resin sheet is excellent in flexibility (handling property).
(2) Excellent adhesion between the insulating layer and the conductor layer formed on the surface thereof.
(3) The substrate surface roughness is small.
(4) It has a high glass transition temperature.

One aspect of the present invention is a resin sheet including an outer layer that is one type selected from the group consisting of a polymer film, a metal foil, and a metal film, and an insulating layer laminated on the outer layer, The insulating layer is a resin sheet containing the components (A) to (E).

Hereinafter, the present invention will be described in detail. In the present invention, “X to Y” includes X and Y which are their end values. “X or Y” means either X or Y or both.

In the present invention, a composition containing components (A) to (E) and other components described later as required is referred to as a “resin composition”. A layer provided on the outer layer and containing the resin composition and having no fluidity at room temperature is referred to as an “insulating layer”. As will be described later, the insulating layer may contain a solvent. Further, since the insulating layer is used by being bonded to another material, it needs to be curable. Specifically, the curable resin in the insulating layer is uncured or partially reacted but is curable. A fluid having fluidity that contains the resin composition and a solvent and can be applied to the outer layer at room temperature is referred to as “varnish”. Hereinafter, each component will be described.

[I-1. Epoxy compound (A)]
The epoxy compound (A) used in the present invention is an organic compound having at least one epoxy group. The number of epoxy groups per molecule of the epoxy compound (A) is 1 or more. The number of the epoxy groups is more preferably 2 or more.

A conventionally well-known epoxy resin can be used as an epoxy compound (A). As for an epoxy compound (A), only 1 type may be used and 2 or more types may be used together.

Examples of the epoxy compound (A) include a biphenyl aralkyl type epoxy compound (epoxy group-containing biphenyl aralkyl resin), a naphthalene type epoxy compound (an epoxy group-containing compound having a naphthalene skeleton: a naphthalene bifunctional epoxy compound), and a bisnaphthalene type epoxy. Compound (epoxy group-containing compound having bisnaphthalene skeleton: naphthalene tetrafunctional epoxy compound), aromatic hydrocarbon formaldehyde type epoxy compound (epoxy group-containing aromatic hydrocarbon formaldehyde resin), anthraquinone type epoxy compound (epoxy having anthraquinone skeleton) Group-containing compound), naphthol aralkyl type epoxy compound (epoxy group-containing naphthol aralkyl resin), zylock type epoxy compound (epoxy group-containing zylock resin), Sphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolak type epoxy resin, trifunctional phenol type epoxy compound (epoxy group-containing compound having trifunctional phenol skeleton), tetrafunctional phenol type epoxy compound (tetrafunctional phenol skeleton) Epoxy group-containing compound), biphenyl type epoxy resin (epoxy group-containing compound having biphenyl skeleton), aralkyl novolak type epoxy resin, triazine skeleton epoxy compound (triazine skeleton containing epoxy resin) alicyclic epoxy resin, polyol type epoxy resin A compound obtained by epoxidizing a double bond of a double bond-containing compound such as glycidylamine, glycidyl ester, and butadiene, and a reaction of a hydroxyl group-containing silicone resin with epichlorohydrin. That compound, and the like.

As described in the above examples, in this specification, an epoxy compound having a structure obtained by epoxidizing a certain resin or compound is referred to as “˜epoxy compound” in the name of the resin or compound. May be expressed.

Among these, as the epoxy compound (A), biphenylaralkyl type epoxy compound, naphthalene type epoxy compound, bisnaphthalene type epoxy compound, aromatic from the viewpoints of adhesion between the insulating layer and the plated conductor layer and flame retardancy Hydrocarbon formaldehyde epoxy compounds (preferred examples include aromatic hydrocarbon formaldehyde resins obtained by polymerizing aromatic hydrocarbons such as benzene, toluene and xylene with formaldehyde, and hydroxyl-containing aromatic carbonization such as phenol and xylenol. Compounds modified with hydrogen and further epoxidized with hydroxyl groups, compounds with epoxidized hydroxyl groups of aromatic hydrocarbon formaldehyde resins obtained by polymerizing hydroxyl-containing aromatic hydrocarbons such as phenol and xylenol with formaldehyde, etc. ), Anthraquinone Epoxy compounds, naphthol aralkyl-type epoxy compounds, and xylok type epoxy compound is preferably one or more members selected from the group consisting of.

The biphenyl aralkyl type epoxy compound is preferably a compound represented by the formula (1). By using this preferable biphenyl aralkyl type epoxy compound, the combustion resistance of the insulating layer can be improved.

(In the formula, each R ¹ independently represents a hydrogen atom or a methyl group. N ¹ represents an integer of 1 or more.)

The content of the epoxy compound (A) in the present invention is not particularly limited, but from the viewpoint of heat resistance and curability, the range of 20 to 80 parts by mass is preferable with respect to 100 parts by mass of the resin solid content of the insulating layer, preferably 30 to 70. The range of parts by mass is particularly suitable. Here, the “resin solid content of the insulating layer” is a component excluding the inorganic filler (C) in the insulating layer. As will be described later, when the insulating layer is manufactured with varnish, the insulating layer may contain a solvent. In this case, the resin solid content in the insulating layer is a component excluding the inorganic filler (C) and the solvent. Therefore, the resin solid content of 100 parts by mass means that when the inorganic filler (C) and the solvent in the insulating layer are included, the total of components excluding the solvent is 100 parts by mass.

As the epoxy compound (A), off-the-shelf products having various structures are commercially available, and they can be appropriately obtained and used. Moreover, you may manufacture an epoxy compound (A) using a well-known various manufacturing method. Examples of such a production method include a method of obtaining or synthesizing a hydroxyl group-containing compound having a desired skeleton, modifying the hydroxyl group by a known method, and epoxidizing (introducing an epoxy group).

[I-2. Cyanate ester compound (B)]
The cyanate ester compound (B) used in the present invention is not particularly limited as long as it is a compound having a cyanate group (cyanate ester group). Specifically, naphthol aralkyl type cyanate ester compound (cyanate group-containing naphthol aralkyl resin), aromatic hydrocarbon formaldehyde type cyanate ester compound (cyanate group-containing aromatic hydrocarbon formaldehyde resin), biphenyl aralkyl type cyanate ester compound (Cyanato group-containing biphenyl aralkyl resin), novolac-type cyanate ester compound (cyanato group-containing novolak resin), and the like.

These cyanate ester compounds (B) impart excellent properties such as high chemical resistance, high glass transition temperature, and low thermal expansion in the insulating layer of the present invention, and therefore can be suitably used in the present invention. .

In addition, as described in the above examples, in this specification, a cyanate ester compound (B) having a structure obtained by cyanating (cyanate esterification) a certain resin or compound is referred to as the name of the resin or compound. It may be indicated with the description “-type cyanate ester compound”.

Among these, as the cyanate ester compound (B), a naphthol aralkyl type cyanide is provided from the viewpoint of providing the insulating layer of the present invention having excellent flame retardancy, high curability, and high glass transition temperature of the cured product. Acid ester compound, aromatic hydrocarbon formaldehyde type cyanate ester compound (preferably, aromatic hydrocarbon formaldehyde resin obtained by polymerizing aromatic hydrocarbon such as benzene, toluene, xylene and the like with formaldehyde, phenol, Hydroxyl group-containing aromatic hydrocarbon formaldehyde obtained by polymerizing hydroxyl group-containing aromatic hydrocarbons such as phenol and xylenol with formaldehyde modified with hydroxyl group-containing aromatic hydrocarbons such as xylenol and further hydroxylating the hydroxyl group Compounds in which the hydroxyl group of the resin is cyanated ), And one member selected from the group consisting of biphenyl aralkyl type cyanate ester compound, or two or more are particularly preferred.

As the naphthol aralkyl type cyanate ester compound, a compound represented by the formula (2) is preferable.

(In the formula, each R ² independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable. N ² represents an integer of 1 or more.)

As the novolac-type cyanate ester compound, a compound represented by the formula (3) or the formula (4) is preferable.

(In the formula, R ³ represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable. N ³ represents an integer of 1 or more.)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable. N ⁴ represents an integer of 1 or more.)

The content of the cyanate ester compound (B) in the present invention is not particularly limited, but is preferably in the range of 20 to 40 parts by mass with respect to 100 parts by mass of the resin solid content of the insulating layer, from the viewpoint of heat resistance and curability. A range of 25 to 35 parts by mass is particularly suitable.

As the cyanate ester compound (B), off-the-shelf products with various structures are commercially available, and can be obtained and used as appropriate. Moreover, you may manufacture a cyanate ester compound (B) using a well-known various manufacturing method. Examples of such production methods include a method of obtaining or synthesizing a hydroxyl group-containing compound having a desired skeleton, and modifying the hydroxyl group by a known method to form cyanate. Examples of the method for cyanating a hydroxyl group include the method described in Ian Hamerton, “Chemistry and Technology of Cyanate Ester Resins,” “Blackie Academic & Professional”.

[I-3. Inorganic filler (C)]
The inorganic filler (C) used in the present invention is not particularly limited, but examples include silica (for example, natural silica, fused silica, amorphous silica, hollow silica, etc.), an aluminum compound (for example, boehmite, aluminum hydroxide, Alumina etc.), magnesium compounds (eg magnesium oxide, magnesium hydroxide etc.), calcium compounds (eg calcium carbonate etc.), molybdenum compounds (eg molybdenum oxide, zinc molybdate etc.), talc (eg natural talc, calcined talc etc.), Examples include mica (mica), glass (for example, short fiber glass, spherical glass, fine powder glass (for example, E glass, T glass, D glass, etc.)) and the like. These inorganic fillers (C) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

Among these, the inorganic filler (C) is preferably one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, magnesium oxide and magnesium hydroxide.

Particularly, from the viewpoint of low thermal expansion, silica is preferable as the inorganic filler (C), and among them, fused silica is particularly preferable. Specific examples of the fused silica include SFP-130MC manufactured by Denki Kagaku Kogyo Co., Ltd., SC2050-MB, SC2500-SQ, SC4500-SQ manufactured by Admatechs Co., Ltd., and the like.

Also, as the inorganic filler (C), it is also preferable to use magnesium hydroxide or magnesium oxide alone or in combination with other inorganic fillers such as silica. Magnesium hydroxide and magnesium hydroxide have the effect of improving the flame resistance. Specific examples of magnesium hydroxide include “Echo Mug Z-10” and “Echo Mug PZ-1” manufactured by Tateho Chemical Co., Ltd., “Magsees N”, “Magsees S” manufactured by Kamishima Chemical Co., Ltd., “ “Magsees EP”, “Magsees EP2-A”, MGZ-1, MGZ-3, MGZ-6R manufactured by Sakai Chemical Industry Co., Ltd., “Kisuma 5”, “Kisuma 5A” manufactured by Kyowa Chemical Industry Co., Ltd., “ Kisma 5P "and the like. Specific examples of magnesium oxide include FNM-G manufactured by Tateho Chemical Industry Co., Ltd., SMO, SMO-0.1, SMO-S-0.5 manufactured by Sakai Chemical Industry Co., Ltd., and the like.

The average particle diameter of the inorganic filler (C) is not limited, but is preferably 0.01 to 5.0 μm and more preferably 0.2 to 2.0 μm from the viewpoint of improving the productivity of the resin sheet. In the present specification, the “average particle diameter” of the inorganic filler (C) means the median diameter of the inorganic filler (C). Here, the median diameter refers to the number or mass of particles on the larger particle size side and the number on the smaller particle size side when the particle size distribution of the powder is divided into two based on a certain particle size. The mass means a particle size that occupies 50% of the total powder. The average particle diameter (median diameter) of the inorganic filler (C) is measured by a wet laser diffraction / scattering method.

The content of the inorganic filler (C) in the present invention is not limited, but from the viewpoint of obtaining high plating peel strength while reducing the thermal expansion of the insulating layer, the resin solid content of 100 parts by mass of the insulating layer, The amount is preferably 50 to 300 parts by mass, and more preferably 70 to 250 parts by mass. In addition, when using together 2 or more types of inorganic fillers (C), it is preferable that these total amount satisfy | fills the said ratio.

[I-4. First acrylonitrile-butadiene rubber (D) having a weight average molecular weight of 100,000 or more]
The first acrylonitrile-butadiene rubber (D) used in the present invention is uncrosslinked and has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100,000 or more. .

The first acrylonitrile-butadiene rubber (D) preferably has a Mooney viscosity of 20 or more. Here, Mooney viscosity (ML1 + 4,100 ° C.) is a viscosity measured in accordance with JISK6300-1, using an L rotor, with a preheating time of 1 minute, a rotor operating time of 4 minutes, and a temperature of 100 ° C. It is an index to represent. When the torque acting on the rotor shaft is 8.30 N · m, 100 (Mooney unit) and when 0.083 N · m is 1 (Mooney unit), the Mooney viscosity and torque are in a linear relationship. The Mooney viscosity can be calculated from the measured torque. Examples of the first acrylonitrile-butadiene rubber (D) include N220S manufactured by JSR Corporation.

The content X of the first acrylonitrile-butadiene rubber (D) in the present invention is not particularly limited, but from the viewpoint of obtaining flexibility while reducing the thermal expansion of the insulating layer, the resin solid content of the insulating layer is 100 mass. Preferably, 0 <X <15 parts by mass, and more preferably 3 <X <10 parts by mass. When two or more kinds of the first acrylonitrile-butadiene rubber (D) are used in combination, the total amount of these preferably satisfies the above ratio.

Acrylonitrile in the first acrylonitrile-butadiene rubber (D) is preferably 37 to 43% by mass from the viewpoint of the flexibility of the resin sheet and the adhesion between the insulating layer and the conductor layer formed on the surface thereof. . The first acrylonitrile-butadiene rubber (D) preferably has no functional group. This is because the functional group causes cross-linking and reduces the flexibility of the rubber. Examples of the functional group include a carboxyl group, an epoxy group, a vinyl group, and an amino group.

[I-5. Second acrylonitrile-butadiene rubber (E) having a weight average molecular weight of 1,000 to 30,000]
The second acrylonitrile-butadiene rubber (E) used in the present invention is uncrosslinked and has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. 1,000 to 30,000. The second acrylonitrile-butadiene rubber (E) preferably has a Mooney viscosity of 1 or less. Examples of the second acrylonitrile-butadiene rubber (E) include N280 manufactured by JSR Corporation.

The acrylonitrile content in the second acrylonitrile-butadiene rubber (E) may be the same as the content in (D), but is preferably 25 to 35% by mass from the viewpoint of availability. Similarly to the component (D), the second acrylonitrile-butadiene rubber (E) preferably has no functional group.

The content Y of the second acrylonitrile-butadiene rubber (E) in the present invention is not limited, but from the viewpoint of obtaining flexibility while reducing the thermal expansion of the insulating layer, the resin solid content of the insulating layer is 100 parts by mass. On the other hand, 0 <Y <15 parts by mass is preferable, and 3 <Y <10 parts by mass is more preferable. When two or more kinds of the second acrylonitrile-butadiene rubber (E) are used in combination, the total amount of these preferably satisfies the above ratio.

When the mass part of the first acrylonitrile-butadiene rubber (D) in the present invention is X and the mass part of the second acrylonitrile-butadiene rubber (E) is Y, the total content X + Y is not particularly limited, From the viewpoint of obtaining flexibility while improving the compatibility of acrylonitrile-butadiene rubber in the resin, it is preferable that 0 <X + Y <15 parts by mass with respect to 100 parts by mass of the resin solid content of the insulating layer. More preferably, <X + Y <10 parts by mass.

Although the ratio of X and Y is not limited, X: Y = 1: (0.5 to 2) is preferable, and X: Y = 1: (0.8 to 1.2) is more preferable.

In the present invention, two kinds of acrylonitrile-butadiene rubbers having different molecular weights and viscosities are used. That is, the insulating layer of the present invention includes acrylonitrile-butadiene rubber having a bimodal molecular weight distribution. Thereby, excellent flexibility and low surface roughness can be imparted to the resin sheet. Although this reason is not limited, it is guessed as follows. Although high stress relaxation is achieved by the high molecular weight component (D) and flexibility is improved, it is easy to aggregate when it is only this, and it is easy to collapse as a large lump from the sheet surface, and the surface roughness becomes high. However, the combined use of the low molecular weight component (E) makes it possible to moderately suppress the aggregation of (D).

[I-6. Maleimide Compound (F)]
In the present invention, it is preferable to use the maleimide compound (F) when improving the moisture absorption heat resistance of the insulating layer. The maleimide compound (F) used is not particularly limited as long as it is a compound having a maleimide group, and specifically, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimide) Phenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimide) Phenyl) methane, tris (4-maleimidophenyl) methane, a maleimide compound represented by the formula (5), a long-chain alkyl bismaleimide represented by the formula (6), and the like.

Among these, the maleimide compound represented by the formula (5) is preferable from the viewpoint of moisture absorption heat resistance and flame resistance. Commercially available products can be used as the compound, and examples thereof include KMI Kasei Co., Ltd. BMI-2300.

(In the formula, each R ⁵ independently represents a hydrogen atom or a methyl group. N ⁵ is in the range of 1 to 10 as an average value.)

Further, from the viewpoint of obtaining high plating peel strength, it is preferable to use a long-chain alkyl bismaleimide represented by the formula (6). Commercially available products can be used as the compound, and examples thereof include BMI-1000P manufactured by KAI Kasei Co., Ltd.

(Wherein n ⁶ represents an integer of 1 to 30)

In addition, it can also mix | blend in the form of the prepolymer of these maleimide compounds, or the prepolymer of a maleimide compound and an amine compound, and it is also possible to mix 1 type (s) or 2 or more types as appropriate.

The content of the maleimide compound (F) in the present invention is preferably 5 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin solid content of the insulating layer. When the amount of bismaleimide is in the range of 5 to 50 parts by mass, good moisture absorption heat resistance can be obtained.

[I-7. Other ingredients
In the present invention, in addition to the components (A) to (E), one or more other components may be contained.

For example, the insulating layer of the present invention may contain a silane coupling agent for the purpose of improving moisture absorption heat resistance. As a silane coupling agent, if it is a silane coupling agent generally used for the surface treatment of an inorganic substance, it will not be limited. Specific examples include aminosilane-based silane coupling agents (for example, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane), and epoxysilane-based silane coupling agents (for example, γ -Glycidoxypropyltrimethoxysilane, etc.), vinylsilane-based silane coupling agents (eg, γ-methacryloxypropyltrimethoxysilane), cationic silane-based silane coupling agents (eg, N-β- (N-vinylbenzyl) Aminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride), phenylsilane-based silane coupling agents, and the like. These silane coupling agents may be used alone or in combination of two or more in any combination and ratio.

When the silane coupling agent is used, its content is not limited, but from the viewpoint of improving moisture absorption heat resistance, the ratio of the silane coupling agent to the inorganic filler (C) is 0.05 to 5% by mass. Preferably, the content is 0.1 to 3% by mass. In addition, when using together 2 or more types of silane coupling agents, it is preferable that these total amount satisfy | fills the said ratio.

The insulating layer of the present invention may contain a wetting and dispersing agent for the purpose of improving the productivity of the resin sheet. The wetting and dispersing agent is not limited as long as it is a wetting and dispersing agent generally used in paints and the like. Specific examples include Disperbyk-110, -111, -180, -161, BYK-W996, -W9010, and -W903 manufactured by Big Chemie Japan. One of these wetting and dispersing agents may be used alone, or two or more thereof may be used in any combination and ratio.

When the wetting dispersant is used, its content is not limited, but from the viewpoint of improving the productivity of the resin sheet, the ratio of the wetting dispersant to the inorganic filler (C) is 0.1 to 5% by mass. Preferably, the content is 0.5 to 3% by mass. In addition, when using 2 or more types of wet dispersing agents together, it is preferable that these total amount satisfy | fills the said ratio.

The insulating layer of the present invention may contain a curing accelerator for the purpose of adjusting the curing speed. As a hardening accelerator, it is well-known as hardening accelerators, such as an epoxy compound and a cyanate ester compound, and if it is generally used, it will not specifically limit. Specific examples include organometallic salts containing metals such as copper, zinc, cobalt, nickel, manganese (for example, zinc octylate, cobalt naphthenate, nickel octylate, manganese octylate, etc.), imidazoles, and derivatives thereof (for example, 2 -Ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole etc.), tertiary amines (eg triethylamine, tributylamine etc.) and the like. These hardening accelerators may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

When the curing accelerator is used, its content is not limited, but from the viewpoint of obtaining a high glass transition temperature, the ratio of the curing accelerator is 0.01 to 5 mass with respect to 100 mass parts of the resin solid content of the insulating layer. Part is preferable, and 0.05 to 4 parts by mass is more preferable. In addition, when using 2 or more types of hardening accelerators together, it is preferable that these total amount satisfy | fills the said ratio.

The insulating layer of the present invention may contain other various polymer compounds or flame retardant compounds as long as the desired properties are not impaired. The polymer compound and the flame retardant compound are not limited as long as they are generally used. Examples of the polymer compound include various thermosetting resins and thermoplastic resins, oligomers thereof, and elastomers. Examples of flame retardant compounds include phosphorus-containing compounds (eg, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins), nitrogen-containing compounds (eg, melamine, benzoguanamine, etc.), oxazine ring-containing compounds, silicone compounds, and the like. Can be mentioned. These polymer compounds or flame retardant compounds may be used alone or in combination of two or more in any combination and ratio.

In addition, the insulating layer of the present invention may contain various additives for various purposes within a range where the intended characteristics are not impaired. Examples of additives include UV absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, Examples include brighteners. These additives may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[I-8. varnish〕
The components (A) to (E) and, if necessary, the other components described above can be dissolved or dispersed in a solvent to obtain a varnish. Such varnish is suitable when producing the resin sheet of this invention mentioned later. The solvent is not limited as long as it can suitably dissolve or disperse the above-described components and does not impair the intended effect of the present invention. Specific examples include alcohols (methanol, ethanol, propanol etc.), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone etc.), amides (eg dimethylacetamide, dimethylformamide etc.), aromatic hydrocarbons (eg toluene) , Xylene, etc.). These organic solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[II-1. Resin sheet)
The resin sheet of the present invention has the above-described insulating layer of the present invention on the outer layer. When manufacturing a printed wiring board using the said resin sheet, you may peel or etch an outer layer from a resin sheet as needed.

The outer layer is not particularly limited, and a polymer film, metal foil, or metal film can be used. Specific examples of the polymer film include polyvinyl chloride, polyvinylidene chloride, polybutene, polybutadiene, polyurethane, ethylene-vinyl oxide copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and other polyesters, polyethylene, polypropylene, and ethylene. -A film containing at least one resin selected from the group consisting of propylene copolymer, polymethylpentene, polyimide and polyamide, and a release film obtained by applying a release agent to the surface of these films, Among these, polyester, polyimide, and polyamide are particularly preferable, and among them, polyethylene terephthalate, which is a kind of polyester, is particularly preferable.

Further, the thickness of the polymer film is not particularly limited, and may be, for example, 0.002 to 0.1 mm. Specific examples of the metal foil or metal film include a foil or film made of a metal such as copper or aluminum. Among them, a copper foil or a copper film is preferable, and an electrolytic copper foil, a rolled copper foil, a copper alloy film, or the like is particularly preferable. Can be used for The metal foil or metal film may be subjected to a known surface treatment such as nickel treatment or cobalt treatment. The thickness of the metal foil or metal film can be appropriately adjusted depending on the intended use, but is preferably in the range of 5 to 70 μm, for example.

The method for producing the resin sheet of the present invention by forming the insulating layer of the present invention on the above outer layer is not limited. For example, the method of apply | coating the above-mentioned varnish on the surface of the above-mentioned outer layer, drying under heating or reduced pressure, removing the solvent, and solidifying the varnish can be mentioned. The drying conditions are not particularly limited, but drying is performed so that the content ratio of the solvent to the total amount of the insulating layer thus formed is usually 10 parts by mass or less, preferably 5 parts by mass or less. The conditions for achieving such drying vary depending on the amount of the organic solvent in the varnish. For example, in the case of a varnish containing 30 to 60 parts by mass of the organic solvent, the drying is performed for about 3 to 10 minutes under heating conditions of 50 to 160 ° C. You can do it. The thickness of the insulating layer in the resin sheet of the present invention is not limited, but it is 0.1 to 500 μm from the viewpoint of better removing light volatiles during drying and more effectively and reliably functioning as a resin sheet. The range of is preferable. When the resin composition does not contain a solvent and has fluidity, the resin composition may be used like a varnish to form an insulating layer.

In addition, when the insulating layer formed from the resin composition having varnish or fluidity is compared with a method formed by a different method (such as melting and pressing the resin), the former is the layer. Excellent uniformity and adhesion to the outer layer.

The resin sheet of the present invention can be used as a build-up material for printed wiring boards. In the printed wiring board formed using the resin sheet of the present invention, the insulating layer of the present invention constitutes the insulating layer in the printed wiring board. The insulating layer in the printed wiring board is usually cured. The printed wiring board will be described in detail below.

[II-2. (Printed wiring board)
The printed wiring board of this invention can be obtained by using the resin sheet of this invention as a buildup material with respect to a core base material. The core substrate is a substrate that becomes a core in the build-up method, and is a metal foil-clad laminate in which the resin insulating layer is completely cured. On the surface of the core substrate, a conductor circuit is formed by a metal foil of a metal foil-clad laminate usually used in the industry, or a conductor layer obtained by peeling and plating the metal foil.

The core base material is mainly a conductive layer (circuit) patterned on one or both sides of a glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like. It means what was done. Further, when the multilayer printed wiring board is manufactured, an intermediate product inner circuit board on which an insulating layer or a conductor layer is to be further formed is also included in the circuit board referred to in the present invention. The surface of the conductor layer (circuit) is preferably subjected to a roughening treatment in advance by a blackening treatment or the like from the viewpoint of adhesion of the insulating layer to the circuit board.

The insulating layer of the resin sheet of the present invention is cured to constitute the insulating layer in the printed wiring board.

Specifically, when using the resin sheet of the present invention as a build-up material, by treating the insulating layer surface of the resin sheet by a conventional method, by forming a wiring pattern (conductor layer) by plating on the insulating layer surface, The printed wiring board of the present invention is obtained.

Other various processes (for example, hole processing for forming via holes, through holes, etc.) may be added as necessary.

Hereinafter, each process for manufacturing the printed wiring board of the present invention will be described.

1) Surface treatment The surface treatment for the insulating layer is performed from the viewpoint of improving the adhesion between the insulating layer and the plated conductor layer, removing smear, and the like. Examples of the surface treatment include desmear treatment and silane coupling treatment. The desmear treatment preferably includes swelling, surface roughening and smear dissolution, and neutralization treatment. The roughening treatment is preferably carried out with a swelling agent and an alkaline oxidizing agent, and the neutralization treatment is preferably carried out with an acidic reducing agent. In the present invention, two acrylonitrile-butadiene rubbers having different molecular weights are used. By subjecting the insulating layer containing this rubber to surface treatment by such a method, collapse marks can be reduced and low surface roughness can be achieved. it can.

It is more preferable that the roughening treatment also serves to remove smear generated by the drilling process. In this case, since the roughening state varies depending on the degree of curing of the insulating layer, it is preferable to select optimum conditions for the later-described lamination molding conditions in combination with the subsequent roughening treatment conditions and plating conditions.

In a preferred embodiment, the roughening treatment first swells the surface insulating layer using a swelling agent. The swelling agent is not limited as long as the wettability of the surface insulating layer is improved and the surface insulating layer can be swollen to the extent that oxidative decomposition is promoted in the next surface roughening and smear dissolution treatment. Examples include alkaline solutions and surfactant solutions.

Next, the swollen surface is treated with an oxidizing agent, and the surface is oxidatively decomposed and roughened. At this time, smear generated in the process is also removed. Examples of the oxidizing agent include an alkaline permanganate solution, and preferred specific examples include an aqueous potassium permanganate solution and an aqueous sodium permanganate solution. Such oxidant treatment is called wet desmear, but in addition to the wet desmear, other known roughening treatments such as dry desmear by plasma treatment or UV treatment, mechanical polishing by buffing, sandblasting, etc. are carried out in an appropriate combination May be.

Further, neutralize the oxidizing agent used in the pretreatment with a reducing agent. Examples of the reducing agent include amine-based reducing agents, and preferred specific examples include acidic aqueous solutions such as hydroxylamine sulfate aqueous solution, ethylenediaminetetraacetic acid aqueous solution, and nitrilotriacetic acid aqueous solution.

In forming a fine wiring pattern, the surface roughness of the insulating layer after the roughening treatment is preferably small. Specifically, the Rz value is preferably 4.0 μm or less, more preferably 2.0 μm or less. Since the surface irregularities after the roughening treatment are determined according to the degree of curing of the insulating layer, the conditions of the roughening treatment, etc., it is preferable to select optimum conditions for obtaining the desired surface irregularities. In particular, the insulating layer of the present invention is extremely suitable because it can ensure adhesion with the plated conductor layer even if the surface roughness is low.

2) Formation of conductor layer Examples of a method for forming a wiring pattern (conductor layer) by plating include a semi-additive method, a full additive method, and a subtractive method. Among these, the semi-additive method is preferable from the viewpoint of forming a fine wiring pattern.

As an example of the pattern forming method by the semi-additive method, after forming a thin conductor layer on the surface of the insulating layer by electroless plating, etc., electrolytic plating is selectively performed using a plating resist (pattern plating), and then the plating resist And a method of forming a wiring pattern by etching an appropriate amount of the whole.

As an example of a method of forming a pattern by a full additive method, there is a method of forming a wiring pattern by performing pattern formation in advance using a plating resist on the surface of an insulating layer and selectively attaching electroless plating or the like.

An example of a pattern forming method using the subtractive method is a method of forming a wiring pattern by forming a conductive layer on the surface of an insulating layer by plating and then selectively removing the conductive layer using an etching resist. It is done. Or when the outer layer of a resin sheet is metal foil or a metal film, these can be etched and a wiring pattern can also be formed.

When forming a wiring pattern by plating, it is preferable to dry after plating from the viewpoint of improving the adhesion strength between the insulating layer and the conductor layer. The pattern formation by the semi-additive method is performed by combining electroless plating and electrolytic plating. In this case, it is preferable to perform drying after the electroless plating and after the electrolytic plating. Drying after electroless plating is preferably performed at 80 to 180 ° C. for 10 to 120 minutes, for example, and drying after electrolytic plating is preferably performed at 130 to 220 ° C. for 10 to 120 minutes, for example. . Since the electroless plating layer is superior to the electroplating layer in layer uniformity, the two can be distinguished.

3) Others In order to manufacture a printed wiring board, the resin sheet of the present invention may be subjected to hole processing. This processing is performed for forming via holes, through holes, and the like. The hole processing is performed by using any one of known methods such as NC drill, carbon dioxide laser, UV laser, YAG laser, plasma, or a combination of two or more if necessary.

The printed wiring board of the present invention can be a multilayer printed wiring board. For example, after forming the laminated board of the present invention that has been subjected to plating treatment, an inner layer circuit is formed thereon, and the resulting circuit is subjected to blackening treatment to obtain an inner layer circuit board. The resin sheet of the present invention is arranged on one side or both sides of the inner layer circuit board thus obtained, and further a metal foil (for example, copper or aluminum) or a release film (polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, A multilayer printed wiring board is manufactured by repeating the operation of disposing a film having a release agent applied to the surface of an ethylenetetrafluoroethylene copolymer film or the like on the outside thereof and performing lamination molding.

Lamination molding uses a technique generally used for lamination molding of ordinary laminates for printed wiring boards, such as a multistage press, a multistage vacuum press, a laminator, a vacuum laminator, an autoclave molding machine, etc., and the temperature is, for example, 100 to 300 C., pressure is, for example, 0.1 to 100 kgf / cm ² (about 9.8 kPa to about 38 MPa), and heating time is appropriately selected within a range of, for example, 30 seconds to 5 hours. If necessary, post-curing may be performed at a temperature of 150 to 300 ° C. to adjust the degree of curing.

Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention in detail, but the present invention is not limited to these.

[Production of cyanate ester compound]
Synthesis Example 1: Synthesis of α-naphthol aralkyl-type cyanate compound (7)

(In the formula, n ⁷ is an average value ranging from 3 to 4.)

A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was previously cooled to 0 to 5 ° C. with a saline solution, to which 7.47 g (0.122 mol) of cyanogen chloride and 35% hydrochloric acid 9. 75 g (0.0935 mol), 76 ml of water, and 44 ml of methylene chloride were charged.

The α-naphthol aralkyl resin represented by the following formula (8) (SN485, OH group equivalent: 214 g / eq. Softening) was maintained with stirring while maintaining the temperature in the reactor at −5 to + 5 ° C. and the pH at 1 or less. Point: A solution prepared by dissolving 20 g (0.0935 mol) of 86 ° C, Nippon Steel Chemical Co., Ltd.) and 14.16 g (0.14 mol) of triethylamine in 92 ml of methylene chloride was added dropwise over 1 hour using a dropping funnel. After completion of the dropwise addition, 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes.

(In the formula, n ⁸ is in the range from 3 to 4 as an average value.)

After completion of dropping, the reaction solution was separated after stirring at the same temperature for 15 minutes, and the organic phase was separated. The obtained organic phase was washed twice with 100 ml of water, and then methylene chloride was distilled off under reduced pressure using an evaporator. Finally, the mixture was concentrated to dryness at 80 ° C. for 1 hour, and expressed by the above formula (7). 23.5 g of cyanate esterified product of α-naphthol aralkyl resin (α-naphthol aralkyl type cyanate ester compound) was obtained.

[Production of varnish and resin sheet]
Example 1
As an epoxy compound (A), a MEK solution (nonvolatile content 70% by mass) of 83.1 parts by mass of a biphenyl aralkyl type epoxy compound (NC-3000-FH, epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd.) (58.2 parts by mass in terms of nonvolatile content), methyl ethyl ketone (hereinafter referred to as the cyanate ester compound (B)) of the α-naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261 g / eq.) Obtained in Synthesis Example 1. "MEK" may be abbreviated.) 58 parts by mass (non-volatile content: 50% by mass) solution (29 mass parts in terms of non-volatile content), novolac maleimide compound (BMI) represented by the following formula (5) as maleimide compound -2300, manufactured by Kay Kasei Co., Ltd.) 4.9 parts by mass, bismaleimide compound (BMI-1000P, Kay A (Made by Kasei Co., Ltd.) 4.9 parts by mass, DMAc solution of 2,4,5-triphenylimidazole (manufactured by Wako Pure Chemical Industries) as a curing accelerator (non-volatile content 20% by mass) 15 parts by mass (3 in terms of non-volatile content) Part by mass) and 0.8 parts by mass (0.08 parts by mass in terms of nonvolatile content) of MEK solution of zinc octylate (nonvolatile content 10% by mass) were dissolved or dispersed in MEK. Subsequently, as the first acrylonitrile-butadiene rubber (D), acrylonitrile-butadiene rubber (N215SL, JSR, weight average molecular weight of about 144,000 (measured by GPC manufactured by Agilent Technologies), Mooney viscosity 45) MEK solution (non-volatile content 20% by mass) 7.5 parts by mass (1.5 parts by mass in terms of non-volatile content), as the second acrylonitrile-butadiene rubber (E), acrylonitrile-butadiene rubber (N280, JSR Co., Ltd.) ), MEK solution (non-volatile component 20 mass%) of 7.5 mass parts (1.5 mass parts in terms of non-volatile content) having a weight average molecular weight of about 9,000 (measured by GPC manufactured by Agilent Technologies). Added. Further, as the inorganic filler (C), 85.7 parts by mass of magnesium oxide MEK slurry (SMO-0.4, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.4 μm, nonvolatile component 70% by mass) 60 parts by mass), phenylaminosilane-treated silica MEK slurry (SC2050-MTX, manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, nonvolatile component 70% by mass) 107.1 parts by mass (in terms of nonvolatile content) 75 parts by mass) was added. After the addition, the mixture is stirred for 30 minutes using a high-speed stirring device, and the epoxy compound (A), the cyanate ester compound (B), the inorganic filler (C), the first acrylonitrile-butadiene rubber (D), the second A varnish containing acrylonitrile-butadiene rubber (E) was obtained. This varnish was applied to a 38 μm thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface and dried by heating at 100 ° C. for 3 minutes to form an insulating layer. A resin sheet having a terephthalate film as an outer layer was obtained.

[Production of inner circuit board]
Glass cloth base material BT resin double-sided copper-clad laminate with inner layer circuit (copper foil thickness 18μm, substrate thickness 0.2mm, Mitsubishi Gas Chemical Co., Ltd. CCL-HL832NX type A) manufactured by MEC The copper surface was roughened by 1 μm etching with CZ8100 to obtain an inner layer circuit board.

[Production of printed wiring board]
The insulating layer surface of the obtained resin sheet was placed on the inner layer circuit board, and after vacuuming (5.0 MPa or less) for 30 seconds using a vacuum laminator (manufactured by Nichigo Morton), the pressure was 10 kgf / cm ² , Lamination molding was performed at a temperature of 100 ° C. for 30 seconds. Furthermore, the printed wiring board was obtained by performing lamination molding for 60 seconds at a pressure of 10 kgf / cm ² and a temperature of 100 ° C. The obtained printed wiring board was dried at 180 ° C. for 60 minutes to sufficiently advance the curing to obtain a printed wiring board.

Example 2
An MEK solution of α-naphthol aralkyl type cyanate ester compound (non-volatile content: 50% by mass) of 55.6 parts by mass (27.8 parts by mass in terms of non-volatile content), biphenyl aralkyl type epoxy compound (NC-3000-FH) The amount of MEK solution (nonvolatile content 70% by mass) used was 79.3 parts by mass (55.5 parts by mass in terms of nonvolatile content), the amount of bismaleimide compound (BMI-1000P) used was 4.6 parts by mass, and novolak maleimide. The amount of compound (BMI-2300) used is 4.6 parts by mass, and the amount of MEK solution (nonvolatile content 20% by mass) of the first acrylonitrile-butadiene rubber (N215SL) is 19 parts by mass (3. 8 parts by mass), and the amount of the second acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used was 19 parts by mass ( Except for in the volatile content basis and 3.8 parts by weight), the same procedure as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Example 3
The amount of MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 54 parts by mass (27 mass parts in terms of non-volatile content), and the MEK of biphenyl aralkyl-type epoxy compound (NC-3000-FH) 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content) of the solution (nonvolatile content 70% by mass), 4.5 parts by mass of the bismaleimide compound (BMI-1000P), novolac maleimide compound The amount of (BMI-2300) used is 4.5 parts by mass, and the amount of the first acrylonitrile-butadiene rubber (N215SL) MEK solution (nonvolatile content 20% by mass) is 25 parts by mass (5.0% in terms of nonvolatile content). Mass part), and the amount of the second acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used is 25 parts by mass ( Except that in volatile content equivalent 5.0 parts by weight) and, in the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Example 4
The amount of α-naphthol aralkyl-type cyanate compound MEK solution (non-volatile content 50% by mass) used was 55.6 parts by mass (27.8 parts by mass in terms of non-volatile content), and the biphenyl aralkyl-type epoxy compound (NC-3000- FH) MEK solution (non-volatile content: 70% by mass) was used in an amount of 79.3 parts by mass (55.5 parts by mass in terms of non-volatile content), and the bismaleimide compound (BMI-1000P) was used in an amount of 4.6 parts by mass. , 4.6 parts by mass of the novolak maleimide compound (BMI-2300) and 9.5 parts by mass (nonvolatile) of the MEK solution of the first acrylonitrile-butadiene rubber (N215SL) (nonvolatile content 20% by mass). 1.9 parts by mass), and the amount of liquid acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used was 28 Except that the amount portion (5.6 parts by mass in terms of a non-volatile component), in the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Example 5
The amount of MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 54 parts by mass (27 mass parts in terms of non-volatile content), and the MEK of biphenyl aralkyl-type epoxy compound (NC-3000-FH) 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content) of the solution (nonvolatile content 70% by mass), 4.5 parts by mass of the bismaleimide compound (BMI-1000P), novolac maleimide compound The amount of (BMI-2300) used is 4.5 parts by mass, and the amount of MEK solution (non-volatile content 20% by mass) of solid acrylonitrile-butadiene rubber (N215SL) is 25 parts by mass (5.0 parts by mass in terms of non-volatile content). ), 25 parts by mass (non-volatile) of MEK solution (non-volatile content 20% by mass) of liquid acrylonitrile-butadiene rubber (N280) Except that the amount of phenylaminosilane-treated silica MEK slurry (SC2050-MTX, nonvolatile content 70% by mass) used was 178.6 parts by mass (125% by mass in terms of nonvolatile content). The varnish was adjusted in the same manner as in Example 1 to obtain a resin sheet and a printed wiring board using the resin sheet.

Example 6
The amount of MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 54 parts by mass (27 mass parts in terms of non-volatile content), and the MEK of biphenyl aralkyl-type epoxy compound (NC-3000-FH) 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content) of the solution (nonvolatile content 70% by mass), 4.5 parts by mass of the bismaleimide compound (BMI-1000P), novolac maleimide compound The amount of (BMI-2300) used is 4.5 parts by mass, and the amount of MEK solution (non-volatile content 20% by mass) of solid acrylonitrile-butadiene rubber (N215SL) is 25 parts by mass (5.0 parts by mass in terms of non-volatile content). ), 25 parts by mass (non-volatile) of MEK solution (non-volatile content 20% by mass) of liquid acrylonitrile-butadiene rubber (N280) Except that the amount of phenylaminosilane-treated silica MEK slurry (SC2050-MTX, nonvolatile content 70% by mass) was 285.7 parts by mass (nonvolatile component equivalent 200 parts by mass) The varnish was adjusted in the same manner as in Example 1 to obtain a resin sheet and a printed wiring board using the resin sheet.

Comparative Example 1
The amount of solid acrylonitrile-butadiene rubber (N215SL) MEK solution (non-volatile content 20% by mass) used was 15 parts by mass (3 mass parts in terms of non-volatile content), and liquid acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20). A varnish was prepared in the same manner as in Example 1 except that the amount used was 0 parts by mass to obtain a resin sheet and a printed wiring board using the same.

Comparative Example 2
The amount of the MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 56.8 parts by mass (28.4 parts by mass in terms of non-volatile content), and the biphenyl aralkyl-type epoxy compound (NC-3000- FH) MEK solution (non-volatile content: 70% by mass) was used in an amount of 81.4 parts by mass (57.0 parts by mass in terms of non-volatile content), and the bismaleimide compound (BMI-1000P) was used in an amount of 4.8 parts by mass. , 4.8 parts by mass of the novolak maleimide compound (BMI-2300) and 25 parts by mass of the MEK solution (non-volatile content 20 mass%) of solid acrylonitrile-butadiene rubber (N215SL) (5 in terms of non-volatile content) Mass part), and the amount of liquid acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used is 0 part by mass. Otherwise, in the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Comparative Example 3
The amount of MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 54 parts by mass (27 mass parts in terms of non-volatile content), and the MEK of biphenyl aralkyl-type epoxy compound (NC-3000-FH) 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content) of the solution (nonvolatile content 70% by mass), 4.5 parts by mass of the bismaleimide compound (BMI-1000P), novolac maleimide compound The amount of (BMI-2300) used is 4.5 parts by mass, the amount of the solid acrylonitrile-butadiene rubber (N215SL) MEK solution (nonvolatile content 20% by mass) is 50 parts by mass (10 parts by mass in terms of nonvolatile content), Except for the amount of liquid acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used was 0 parts by mass , In the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Comparative Example 4
The amount of the MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used is 51.0 parts by mass (25.5 parts by mass in terms of non-volatile content), and the biphenyl aralkyl-type epoxy compound (NC-3000- FH) MEK solution (non-volatile content: 70% by mass) was used in an amount of 72.9 parts by mass (51.0 parts by mass in terms of non-volatile content) and the bismaleimide compound (BMI-1000P) was used in an amount of 4.3 parts by mass. The amount of novolak maleimide compound (BMI-2300) used is 4.3 parts by mass, and the amount of solid acrylonitrile-butadiene rubber (N215SL) MEK solution (non-volatile content: 20% by mass) is 75 parts by mass (15% in terms of non-volatile content). Part by mass), and the amount of liquid acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used is 0 part by mass. Other than the can, in the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Comparative Example 5
The amount of solid acrylonitrile-butadiene rubber (N215SL) MEK solution (non-volatile content 20% by mass) used is 0 parts by mass, and the amount of liquid acrylonitrile-butadiene rubber (N280) MEK solution (non-volatile content 20% by mass) used is 15% by mass. The varnish was adjusted in the same manner as in Example 1 except that the content was 3 parts by weight (3 parts by weight in terms of nonvolatile content) to obtain a resin sheet and a printed wiring board using the same.

Comparative Example 6
The amount of the MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 56.8 parts by mass (28.4 parts by mass in terms of non-volatile content), and the biphenyl aralkyl-type epoxy compound (NC-3000- FH) MEK solution (non-volatile content: 70% by mass) was used in an amount of 81.4 parts by mass (57.0 parts by mass in terms of non-volatile content), and the bismaleimide compound (BMI-1000P) was used in an amount of 4.8 parts by mass. , 4.8 parts by mass of novolac maleimide compound (BMI-2300), 0 parts by mass of MEK solution (non-volatile content 20% by mass) of solid acrylonitrile-butadiene rubber (N215SL), liquid acrylonitrile-butadiene rubber The amount of MEK solution (non-volatile content: 20% by mass) of (N280) is 25 parts by mass (5 parts by mass in terms of non-volatile content). Otherwise, in the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Comparative Example 7
The amount of MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used was 54 parts by mass (27 mass parts in terms of non-volatile content), and the MEK of biphenyl aralkyl-type epoxy compound (NC-3000-FH) 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content) of the solution (nonvolatile content 70% by mass), 4.5 parts by mass of the bismaleimide compound (BMI-1000P), novolac maleimide compound The amount of (BMI-2300) used is 4.5 parts by mass, the amount of solid acrylonitrile-butadiene rubber (N215SL) MEK solution (non-volatile content 20% by mass) is 0 part by mass, and liquid acrylonitrile-butadiene rubber (N280) is used. Except for the amount of MEK solution (non-volatile content 20% by mass) used to be 50 parts by mass (non-volatile content equivalent 10 parts by mass) , In the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

Comparative Example 8
The amount of the MEK solution of α-naphthol aralkyl-type cyanate ester compound (non-volatile content 50% by mass) used is 51.0 parts by mass (25.5 parts by mass in terms of non-volatile content), and the biphenyl aralkyl-type epoxy compound (NC-3000- FH) MEK solution (non-volatile content: 70% by mass) was used in an amount of 72.9 parts by mass (51.0 parts by mass in terms of non-volatile content) and the bismaleimide compound (BMI-1000P) was used in an amount of 4.3 parts by mass. The amount of novolak maleimide compound (BMI-2300) used is 4.3 parts by mass, the amount of solid acrylonitrile-butadiene rubber (N215SL) MEK solution (nonvolatile content 20% by mass) is 0 parts by mass, and liquid acrylonitrile-butadiene rubber 75 parts by mass (15 parts by mass in terms of nonvolatile content) of MEK solution (N280) (N20) Other than the can, in the same manner as in Example 1 to adjust the varnish, to give a resin sheet and a printed wiring board using the same.

[Evaluation of resin sheet]
(1) Flexibility Using the resin sheets produced by the procedures of Examples 1 to 6 and Comparative Examples 1 to 8, in order to confirm the handleability of the resin sheet, the obtained resin sheet 100 mm × 100 mm sample was 180. The sample was bent and visually observed for the occurrence of cracks. The thing in which the crack did not generate | occur | produced was set to "a". Subsequently, for those with cracks, visually observed whether cracks occur when a resin sheet is wrapped around a 15 mm diameter rod. The thing in which the crack did not generate | occur | produced was set as "b". The case where cracks occurred in all the above evaluations was designated as “c”. The results are shown in Table 1.

[Evaluation of printed wiring board]
Wet roughening treatment of printed wiring board and conductor layer plating The outer layer was peeled from the printed wiring boards obtained in Examples 1 to 6 and Comparative Examples 1 to 8. Electroless copper plating process (used chemical name: MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver. 2) manufactured by Uemura Kogyo Co., Ltd. on the exposed insulating layer Then, electroless copper plating of about 0.8 μm was applied and dried at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 18 μm, and drying was performed at 180 ° C. for 1 hour. In this way, a sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was prepared and subjected to the following evaluation.

(2) Plating copper adhesive force Using the sample prepared by the above procedure, the adhesive strength of the plated copper was measured three times according to JIS C6481, and the average value was obtained. About the sample swollen by the drying after electrolytic copper plating, it evaluated using the part which is not swollen. The results are shown in Table 1.

(3) Surface roughness After etching the surface layer plated copper of the sample prepared by the above procedure, the Rz (10-point average roughness) of the insulating layer surface was measured by using a laser microscope (VK-9500, manufactured by Keyence) at a magnification of 3000 times. ) And Ra (arithmetic mean roughness). The results are shown in Table 1.

(4) Maximum Collapse Size The sample prepared by the above procedure is roughened in the electroless plating process, and forms a collapse mark in which the acrylonitrile-butadiene rubber has fallen off when the roughening solution is eroded. Using SEM-EDX (JEOL's JSM-6460LA), the image with the maximum collapse mark diameter was selected from the 1000 × image and the 10,000 × image, and the maximum collapse size was determined. The results are shown in Table 1.

(5) Glass transition temperature (Tg)
Using a resin sheet with an insulating layer thickness of 0.05 mm cured at 180 ° C. for 2 hours, the temperature was raised from 25 ° C. to 250 ° C. at 10 ° C. per minute with a thermomechanical analyzer (TA Instruments Q800), and glass The transition temperature was measured. The results are shown in Table 1.

As described above, when the resin sheet of the present invention is used as a material for an insulating layer of a printed wiring board, various effects such as excellent handling of the resin sheet and excellent adhesion between the insulating layer and the plated conductor layer, etc. Therefore, it is extremely useful as a material for an insulating layer of a printed wiring board.

Claims

A resin sheet comprising an outer layer that is one type selected from the group consisting of a polymer film, a metal foil and a metal film, and an insulating layer laminated on the outer layer,
The insulating layer is an epoxy compound (A), a cyanate ester compound (B), an inorganic filler (C), and a first acrylonitrile-butadiene rubber (D) having a weight average molecular weight measured by GPC of 100,000 or more. And a second acrylonitrile-butadiene rubber (E) having a weight average molecular weight of 1,000 to 30,000.
The resin sheet according to claim 1, wherein the content X of the first acrylonitrile-butadiene rubber (D) is 0 <X <15 parts by mass with respect to 100 parts by mass of the resin solid content.
3. The resin sheet according to claim 1, wherein the content Y of the second acrylonitrile-butadiene rubber (E) is 0 <Y <15 parts by mass with respect to 100 parts by mass of the resin solid content.
The total X + Y of the content X of the first acrylonitrile-butadiene rubber (D) and the content Y of the second acrylonitrile-butadiene rubber (E) is 0 <X + Y <15 with respect to 100 parts by mass of the resin solid content. The resin sheet according to any one of claims 1 to 3, which is a part by mass.
The resin sheet according to any one of claims 1 to 4, wherein the insulating layer further contains a maleimide compound (F).
The resin sheet according to any one of claims 1 to 5, wherein the polymer film is any one selected from the group consisting of polyester, polyimide and polyamide.
The insulating layer is obtained by applying a resin composition containing the components (A) to (E) on the outer layer, and then drying and solidifying by heating or under reduced pressure. The resin sheet as described in any one of these.
A printed wiring board comprising the insulating layer according to any one of claims 1 to 7, which is laminated on a circuit board having a core base material and a conductor circuit formed on the core base material.
The printed wiring board according to claim 8, wherein the insulating layer is surface-treated and includes a conductor layer patterned on the surface.
10. The printed wiring board according to claim 9, wherein the surface treatment is a desmear treatment including a roughening treatment with a swelling agent and an alkaline oxidizing agent and a neutralization treatment with an acidic reducing agent.
The printed wiring board according to claim 9 or 10, wherein the conductor layer includes a conductor layer formed by a semi-additive method or a conductor layer formed by a subtractive method.
The printed wiring board according to claim 9 or 10, wherein the conductor layer includes a conductor layer obtained by etching an outer layer made of the metal foil or metal film according to claim 1.