TW201636211A - Resin sheet and print circuit board - Google Patents

Abstract

To provide a resin sheet comprising a resin composition that is used for an insulating layer of a print circuit board and provides a good handling ability to the resin sheet and a good adhesiveness to a conductive layer provided on the insulating layer.A resin sheet comprising an outer layer comprising at least one material selected from the group consisting of a polymer film, metal foil, and metal film, and an insulating layer laminated on the outer layer, which insulating layer comprises (A) epoxy compound, (B) cyanate ester compound, (C) inorganic filler, (D) first acrylonitril-butadiene rubber having weight-average molecular weight of 100,000 or more determined by GPC, and (E) second acrylonitril-butadiene rubber having the weight-average molecular weight of 1,000 to 30,000.

Description

Resin sheet and printed circuit board

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

In recent years, miniaturization and high performance of electronic devices are progressing. In the multilayer printed circuit board, in order to improve the mounting density of electronic components, the miniaturization of the conductor wiring has progressed, and it is desired to have a wiring forming technique. As a method of forming a high-density fine wiring on an insulating layer, there is known an additive method in which a conductor layer is formed only by electroless plating, and electroless plating is used to form a conductor by electrolytic plating after forming a copper thin layer in an all-round manner. The layer, followed by a semi-additive method of rapidly etching the copper thin layer.

Since the rapid etching process in the subsequent step cannot remove the plating of the deep portion of the physical anchor, it is desirable that the roughness of the surface of the insulating layer be as small as possible. On the other hand, when the roughness of the surface of the insulating layer is small, the adhesion strength between the conductor layer and the insulating layer tends to be small. Therefore, it is desirable to have an insulating layer resin composition having a high adhesion strength to the interface of the conductor layer even if the roughness of the surface of the insulating layer is small.

In addition, due to the miniaturization and high density of multilayer printed wiring boards, research on thinning of laminated boards used for multilayer printed wiring boards has been actively conducted. With the reduction in the thickness of the multilayer printed wiring board, the insulating layer is also required to be thinner, and it is desired to study a resin sheet which does not contain a glass cloth and has good handleability. With the reduction in thickness, there is a problem that the mounting reliability is lowered and the warpage of the multilayer printed wiring board is increased. Therefore, a resin composition to be an insulating layer material is required to have high adhesion and a high glass transition temperature.

In response to this request, various means have been taken. For example, Patent Document 1 discloses a technique of adding a liquid rubber in order to improve crack resistance from the viewpoint of improving workability. Specifically, this document discloses a resin composition comprising: (A) a polymerization of a ring-containing structure of a hydrogenated ring-opening polymer of a norbornene-based monomer having a functional group of at least one of an acid anhydride group and a carboxyl group The resin, (B) an epoxy compound as a curing agent, (C) an imidazole compound having a substituent having a ring structure, and (D) a liquid rubber having a liquid polybutadiene.

Patent Document 2 discloses a technique of using a rubber component in order to improve adhesion. It is described that the rubber component may be solid or liquid at room temperature (25 ° C), but it is preferably liquid in view of improving fluidity.

Patent Document 3 describes a cured product of a curable resin composition containing a mixture of a cyanate resin composition and an acrylonitrile-butadiene copolymer or a preliminary reaction product, which is excellent in flexibility and has good elasticity. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4277440 (Patent Document 2) International Publication No. 2013/042724 (Patent Document 3) Japanese Patent Laid-Open No. 56-157424

[Questions to be solved by the invention]

Although the method described in Patent Document 1 can improve crack resistance, this document does not describe the concept of high glass transition temperature at all.

Further, although the method described in Patent Document 2 is excellent in adhesion and fluidity, the flexibility of the resin sheet in a semi-hardened state is not described at all.

Further, in Patent Document 3, it is described that the resin sheet obtained from the resin composition is excellent in flexibility and elasticity, but the flexibility of the resin sheet in a semi-hardened state is not described at all. Moreover, the concept of the adhesion between the conductor layer and the resin layer by plating is not described at all.

The present invention has been made in view of the above problems, and it is an object of the invention to provide a resin sheet which is excellent in handleability when used for an insulating layer of a printed circuit board material, and which is excellent in adhesion between an insulating layer and a conductor layer formed by plating a surface thereof. The glass transition temperature is high when it is completely hardened; and a printed circuit board using the resin sheet is provided. [How to solve the problem]

The inventors of the present invention have diligently studied and found that an outer layer which is selected from any group consisting of a polymer film, a metal foil, and a metal film, and an insulating layer laminated on the outer layer, and The insulating layer contains the epoxy compound (A), the cyanate ester compound (B), the inorganic filler (C), and the first acrylonitrile-butadiene rubber (D) having a weight average molecular weight of 100,000 or more as measured by GPC. The resin sheet of the acrylonitrile-butadiene rubber (E) having a weight average molecular weight of 1,000 to 30,000 can solve the above problems, and the present invention has been completed.

[1] A resin sheet comprising: an outer layer 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 containing a ring Oxygen compound (A), cyanate ester compound (B), inorganic filler (C), first acrylonitrile-butadiene rubber (D) having a weight average molecular weight of 100,000 or more as measured by GPC, and the weight average molecular weight It is the second acrylonitrile-butadiene rubber (E) of 1,000 to 30,000. [2] The resin sheet of [1], wherein the content X of the first acrylonitrile-butadiene rubber (D) is 0 < X < 15 parts by mass based on 100 parts by mass of the resin solid content. [3] The resin sheet according to [1] or [2], wherein the content Y of the second acrylonitrile-butadiene rubber (E) is 0 < Y < 15 parts by mass based on 100 parts by mass of the resin solid content. [4] The resin sheet according to any one of [1] to [3] wherein the content of the first acrylonitrile-butadiene rubber (D) is X and the second acrylonitrile-butadiene rubber (E) The total content of the components Y, X + Y, is 0 < X + Y < 15 parts by mass based on 100 parts by mass of the resin solid content. [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 selected from the group consisting of polyester, polyimine, and polyamine. [7] The resin sheet according to any one of [1] to [6] wherein the insulating layer is applied to the outer layer after coating the resin composition containing the components (A) to (E), or It is dried under reduced pressure and solidified. [8] A printed circuit board comprising the insulating layer of any one of [1] to [7] laminated on a circuit substrate having a core substrate and a conductor circuit formed on the core substrate. [9] The printed circuit board of [8], wherein the insulating layer is surface-treated, and a patterned conductor layer is provided on the surface. [10] The printed circuit board according to [9], wherein the surface treatment is a stain removal treatment comprising a roughening treatment using a swelling agent and an alkali oxidizing agent, and a neutralization treatment using an acidic reducing agent. [11] The printed circuit board of [9] or [10], wherein the conductor layer comprises a conductor layer formed by a semi-additive method or a conductor layer formed by subtraction. [12] The printed circuit board of [9] or [10], wherein the conductor layer comprises a conductor layer obtained by etching a layer formed of a metal foil or a metal film as in the first aspect of the patent application. [Effects of the Invention]

The resin sheet of the present invention exhibits at least one of the following effects (1) to (4), and preferably exhibits all of them. (1) The resin sheet is excellent in flexibility (operability). (2) The insulating layer is excellent in adhesion to the conductor layer formed by plating on the surface. (3) The surface roughness of the substrate is small. (4) The glass transition temperature is high.

An aspect of the invention is a resin sheet comprising: an outer layer 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 contains the above components (A) to (E).

The invention is described in detail below. In the present invention, "X~Y" includes its ends X and Y. "X or Y" represents either X, Y, or both.

In the present invention, the composition including the components (A) to (E) and other components described later is referred to as a "resin composition". A layer which is provided on the outer layer and includes a resin composition, and which has no fluidity at room temperature, is called an "insulation layer". As will be described later, the insulating layer may contain a solvent. Moreover, since the insulating layer is adhered to and used by other materials, it must be hardenable. Specifically, the curable resin in the insulating layer is in a state of being unhardened or partially reacted but hardenable. A liquid containing the above-mentioned resin composition and solvent and having fluidity which can be applied to the outer layer at room temperature is called "varnish". The following describes each component.

[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 preferably 2 or more.

As the epoxy compound (A), a conventionally known epoxy resin can be used. The epoxy compound (A) may be used alone or in combination of two or more.

Epoxy compound (A), for example, biphenyl aralkyl type epoxy compound (epoxy group-containing biphenyl aralkyl resin), naphthalene type epoxy compound (epoxy group-containing compound having naphthalene skeleton: naphthalene Bifunctional epoxy compound), double naphthalene epoxy compound (epoxy group-containing compound having naphthalene skeleton: naphthalene 4-functional epoxy compound), aromatic hydrocarbon formaldehyde type epoxy compound (containing epoxy group aromatic) Group hydrocarbon epoxy resin), oxime type epoxy compound (epoxy group-containing compound having an anthracene skeleton), naphthol aralkyl type epoxy compound (epoxy group-containing naphthol aralkyl resin), Xyloc Type epoxy compound (Xyloc resin containing epoxy group), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin, trifunctional phenol type epoxy compound (having 3 a functional group of a functional epoxy group containing an epoxy group), a tetrafunctional phenol type epoxy compound (an epoxy group-containing compound having a tetrafunctional phenol skeleton), and a biphenyl type epoxy resin (having an epoxy group having a biphenyl skeleton) Compound), aralkyl novolac type epoxy resin, three Skeleton epoxy compound (containing three Epoxy resin of the skeleton) a cycloaliphatic epoxy resin, a polyhydric alcohol type epoxy resin, a glycidylamine, a glycidyl ester, a compound obtained by epoxidizing a double bond of a compound containing a double bond such as butadiene, and A compound obtained by reacting a hydroxyl group-containing fluorenone resin with epichlorohydrin.

Further, as exemplified above, in the present specification, an epoxy compound having a structure obtained by epoxidizing a certain resin or compound may be expressed by adding a "~ epoxy compound" to the name of the resin or compound.

Among these, the epoxy compound (A) is preferably selected from the group consisting of a biphenyl aralkyl type epoxy compound, from the viewpoints of adhesion between the insulating layer and the plated conductor layer, and flame retardancy. A naphthalene type epoxy compound, a double naphthalene type epoxy compound, or an aromatic hydrocarbon formaldehyde type epoxy compound (preferably, an aromatic hydrocarbon formaldehyde resin obtained by polymerizing an aromatic hydrocarbon such as benzene, toluene or xylene, and formaldehyde is phenol, A compound obtained by modifying a hydroxyl group-containing aromatic hydrocarbon such as xylenol, epoxidizing the hydroxyl group, and polymerizing a hydroxyl group-containing aromatic hydrocarbon such as phenol or xylenol with formaldehyde to obtain an aromatic hydrocarbon formaldehyde resin One or two or more of the group consisting of a quinone type epoxy compound, a naphthol aralkyl type epoxy compound, and a Xyloc type epoxy compound are preferably used in the group in which the hydroxyl group is epoxidized. .

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

【化1】 (wherein R ¹ each independently represents a hydrogen atom or a methyl group. n ¹ represents an integer of 1 or more.)

In the present invention, the content of the epoxy compound (A) is not particularly limited, and from the viewpoint of heat resistance and curability, it is preferably in the range of 20 to 80 parts by mass, more preferably 30 parts by mass based on 100 parts by mass of the resin solid content of the insulating layer. ~70 parts by mass. Here, the "resin solid content of the insulating layer" means a component of the inorganic filler (C) which does not include the insulating layer. As will be described later, when the insulating layer is made of varnish, the insulating layer may include 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, when the insulating layer contains the inorganic filler (C) and the solvent in an amount of 100 parts by mass of the resin solid content, the total amount of the components not including the solvent is 100 parts by mass.

The epoxy compound (A) has been marketed as a finished product of various structures, and these can be suitably obtained and used. Further, the epoxy compound (A) can also be produced by various known methods. For the production method, for example, a method of obtaining or synthesizing a hydroxyl group-containing compound of a desired skeleton, and modifying the hydroxyl group by a known method to epoxidize (introducing an epoxy group) may be mentioned.

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

The cyanate compound (B) can be preferably used in the present invention because it can provide excellent properties such as high chemical resistance, high glass transition temperature, and low thermal expansion property to the insulating layer of the present invention. Further, as exemplified above, in the present specification, a cyanate compound (B) having a structure obtained by subjecting a resin or a compound to cyanooxylation (cyanation) may be used, and the name of the resin or compound may be used herein. The expression "~-type cyanate compound" is added.

Among these, the cyanate ester compound (B) is selected from the viewpoint of providing an insulating layer of the present invention which is excellent in flame retardancy, high in hardenability, and high in glass transition temperature of a cured product, and is selected from naphthol. An aralkyl type cyanate compound or an aromatic hydrocarbon formaldehyde type cyanate compound (for example, an aromatic hydrocarbon formaldehyde resin obtained by polymerizing an aromatic hydrocarbon such as benzene, toluene or xylene and formaldehyde is phenol a compound containing a hydroxyl group-containing aromatic hydrocarbon such as xylenol, a compound which is cyanooxylated with the hydroxyl group, or a hydroxyl group-containing aromatic hydrocarbon such as phenol or xylenol which is polymerized with formaldehyde. One or two or more kinds of the group consisting of a compound of a hydroxy group which is cyanooxylated, and a biphenyl aralkyl type cyanate compound are preferable.

The naphthol aralkyl type cyanate compound is preferably a compound represented by the formula (2).

[Chemical 2] (wherein R ² each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred. n ² represents an integer of 1 or more.)

The novolac type cyanate compound is preferably a compound represented by the formula (3) or the formula (4).

[化3] (wherein R ³ represents a hydrogen atom or a methyl group, of which a hydrogen atom is preferred. n ³ represents an integer of 1 or more.)

【化4】 (wherein R ⁴ represents a hydrogen atom or a methyl group, of which a hydrogen atom is preferred. n ⁴ represents an integer of 1 or more.)

In the present invention, the content of the cyanate ester compound (B) is not particularly limited, and from the viewpoint of heat resistance and hardenability, it is preferably in the range of 20 to 40 parts by mass based on 100 parts by mass of the resin solid content of the insulating layer, 25~ The range of 35 parts by mass is particularly desirable.

The cyanate ester compound (B) has been marketed as a finished product of various structures, and can be suitably obtained and used. Further, the cyanate compound (B) can also be produced by various known methods. This production method is, for example, a method in which a hydroxyl group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxyl group is modified by a known method to be cyanooxylated. A method of cyanooxylation of a hydroxyl group, for example, the method described by 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, and examples thereof include: cerium oxide (for example, natural cerium oxide, molten cerium oxide, amorphous cerium oxide, hollow) Cerium oxide, etc.), aluminum compounds (such as soft boehmite, aluminum hydroxide, aluminum oxide, etc.), magnesium compounds (such as magnesium oxide, magnesium hydroxide, etc.), calcium compounds (such as calcium carbonate, etc.), molybdenum compounds (such as oxidation) Molybdenum, zinc molybdate, etc.), talc (such as natural talc, calcined talc, etc.), mica (mica), glass (for example, short-fibre glass, spherical glass, micro-powder glass (for example, E glass, T glass, D glass, etc.) )and many more. These inorganic fillers (C) may be used singly or in combination of two or more kinds in any combination and in any ratio.

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

In particular, from the viewpoint of low thermal expansion, the inorganic filler (C) is preferably cerium oxide, of which molten cerium oxide is particularly preferred. Specific examples of the molten cerium oxide include SFP-130MC manufactured by Electrochemical Industry Co., Ltd., SC2050-MB, SC2500-SQ, SC4500-SQ manufactured by Admatechs Co., Ltd., and the like.

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

The average particle diameter of the inorganic filler (C) is not limited, and from the viewpoint of improving the manufacturability of the resin sheet, it is preferably 0.01 to 5.0 μm and more preferably 0.2 to 2.0 μm. In the present specification, the "average particle diameter" of the inorganic filler (C) means the intermediate diameter of the inorganic filler (C). Here, the median diameter refers to the number of particles having one side of the larger particle diameter or the number of the mass and the smaller particle diameter when the particle size distribution of the powder is divided into two sides with a certain particle diameter as a reference. Or the masses each account for 50% of the particle size of the whole powder. The average particle diameter (median diameter) of the inorganic filler (C) is measured by a wet laser diffraction/scattering method.

In the present invention, the content of the inorganic filler (C) is not limited, but from the viewpoint of reducing the thermal expansion of the insulating layer and obtaining high plating peel strength, the resin solid content of the insulating layer is preferably 50 to 300 parts by mass. The mass portion is better, and 70 to 250 parts by mass is more preferable. Further, when two or more kinds of inorganic fillers (C) are used in combination, it is preferred that the total amount is in accordance with the above 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 not crosslinked and is infiltrated by a gel. The weight average molecular weight (Mw) measured by chromatography (GPC) was 100,000 or more. The Mooney viscosity of the first acrylonitrile-butadiene rubber (D) is preferably 20 or more. Here, the Mooney viscosity (ML1+4, 100 °C) refers to the index of the representative viscosity measured by the condition of 1 minute of preheating time, 4 minutes of rotor actuation time, and temperature of 100 °C according to JIS K6300-1. . When the torque acting on the shaft of the rotor is 100 (Mini unit) at 8.30 N·m and 1 (Moni unit) at 0.083 N·m, the Mo Ni viscosity has a linear relationship with the torque, so The obtained torque calculates the Mooney viscosity. The first acrylonitrile-butadiene rubber (D) is, for example, N220S manufactured by JSR Co., Ltd., or the like.

In the present invention, the content X of the first acrylonitrile-butadiene rubber (D) is not particularly limited, and it is considered that the thermal expansion of the insulating layer can be reduced and flexibility can be obtained, and 100 parts by mass of the resin solid content of the insulating layer can be obtained. It is preferably 0 < X < 15 parts by mass, and more preferably 3 < X < 10 parts by mass. Further, when two or more kinds of the first acrylonitrile-butadiene rubber (D) are used in combination, it is preferred that the total amount thereof is in accordance with the above ratio.

The acrylonitrile in the first acrylonitrile-butadiene rubber (D) is preferably 37 to 43 in view of flexibility of the resin sheet, adhesion between the insulating layer and the conductor layer formed by plating on the surface thereof, and the like. The mass % is preferred. Further, it is preferred that the first acrylonitrile-butadiene rubber (D) has no functional group. The reason is that the functional group causes cross-linking and the softness of the rubber is lowered. The functional group may, for example, be a carboxyl group, an epoxy group, a vinyl group or an amine group.

[I-5. 2nd 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 tetrahydrofuran is used as a solvent. The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 1,000 to 30,000. The second acrylonitrile-butadiene rubber (E) preferably has a Mooney viscosity of 1 or less. The second acrylonitrile-butadiene rubber (E), for example, N280 manufactured by JSR Co., Ltd., or the like.

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

In the present invention, the content Y of the second acrylonitrile-butadiene rubber (E) is not limited, and the viewpoint of reducing the thermal expansion of the insulating layer and obtaining flexibility is 100% by mass based on the resin solid content of the insulating layer. <Y < 15 parts by mass is more preferable, and 3 < Y < 10 parts by mass is more preferable. Further, when two or more kinds of the second acrylonitrile-butadiene rubber (E) are used in combination, it is preferred that the total amount thereof is in accordance with the above ratio.

In the present invention, when the mass part of the first acrylonitrile-butadiene rubber (D) 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 improving the compatibility of the acrylonitrile-butadiene rubber in the resin and obtaining flexibility, it is preferably 0 < X + Y < 15 parts by mass, and 3 < X + Y < 10 with respect to 100 parts by mass of the resin solid content of the insulating layer. Better quality. The ratio of X to Y is not limited, and it is preferably X:Y=1:(0.5~2), and X:Y=1:(0.8~1.2) is more desirable.

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 comprises an acrylonitrile-butadiene rubber having a bimodal molecular weight distribution. Thereby, excellent flexibility and low surface roughness can be imparted to the resin sheet. Although the reason is not known, it is presumed as follows. When the high molecular weight component (D) is used, high stress relaxation can be achieved and flexibility can be improved. However, if this is the case, it becomes easy to aggregate, and it is easy to collapse from the surface of the sheet in a large manner, and the surface roughness is improved. However, by using the low molecular weight component (E) in combination, the aggregation of (D) can be moderately suppressed.

[I-6. Maleic imine compound (F)] In the present invention, when the moisture absorption heat resistance of the insulating layer is improved, it is preferred to use the maleimide compound (F). The maleated imine compound (F) to be used is not particularly limited as long as it is a compound having a maleimine group, and specific examples thereof include bis(4-maleimidophenyl)methane and 2 , 2-double {4-(4-maleimide phenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, double (3 -ethyl-5-methyl-4-maleimide phenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, ginseng (4-malay) Iminophenyl)methane, a maleic imine compound represented by the formula (5), a long-chain alkyl bismaleimide represented by the formula (6), and the like. Among them, the maleic imine compound represented by the formula (5) is preferred from the viewpoint of moisture absorption heat resistance and flame resistance. Commercially available products can be used as the compound, and examples thereof include BMI-2300 manufactured by KI Chemical Co., Ltd., and the like.

【化5】 (wherein R ⁵ each independently represents a hydrogen atom or a methyl group. n ⁵ is in the range of 1 to 10 in terms of an average enthalpy.)

Further, from the viewpoint of obtaining high plating peel strength, it is preferred to use a long-chain alkyl bismaleimide represented by the formula (6). As the compound, a commercially available product such as BMI-1000P manufactured by KI Chemical Co., Ltd., or the like can be used.

【化6】 (wherein n ⁶ represents an integer of 1 or more and 30 or less.) Further, a prepolymer of the maleimide compound or a prepolymer of the maleimide compound and the amine compound may be blended. One type may be used or two or more types may be used in combination.

In the present invention, the content of the maleic imine compound (F) is preferably 5 to 50 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of the resin solid content of the insulating layer. When the blending amount of the bismaleimide is in the range of 5 to 50 parts by mass, good moisture absorption and heat resistance can be obtained.

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

For example, the insulating layer of the present invention may contain a decane coupling agent in order to improve moisture absorption and heat resistance. The decane coupling agent is not particularly limited as long as it is a decane coupling agent which is generally used for the surface treatment of an inorganic substance. Specific examples thereof include an amino decane-based decane coupling agent (for example, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, etc.) , an epoxy decane decane coupling agent (for example, γ-glycidoxypropyltrimethoxy decane, etc.), a vinyl decane decane coupling agent (for example, γ-methacryloxypropyltrimethoxydecane) Et.), a cationic decane-based decane coupling agent (for example, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane hydrochloride, etc.), phenylnonane decane Coupling agent, etc. These decane coupling agents may be used alone or in combination of two or more kinds in any combination and in any ratio.

When the decane coupling agent is used, the content is not limited, but from the viewpoint of improving moisture absorption and heat resistance, it is preferred to set the ratio of the decane coupling agent to 0.05 to 5% by mass relative to the inorganic filler (C), preferably 0.1 to 0.1%. 3% by mass is better. Further, when two or more kinds of decane coupling agents are used in combination, it is preferred that the total amount is in accordance with the above ratio.

Moreover, the insulating layer of the present invention may contain a wetting dispersant for the purpose of improving the manufacturability of the resin sheet. The wetting dispersing agent is not particularly limited as long as it is a wetting dispersing agent which is generally used in paints and the like. Specific examples include Disperbyk-110, Disperbyk-111, Disperbyk-180, Disperbyk-161, BYK-W996, BYK-W9010, BYK-W903, etc., which are manufactured by BYK Japan Co., Ltd. These wetting dispersing agents may be used singly or in combination of two or more kinds in any combination and in any ratio.

When the wetting dispersing agent is used, the content thereof is not limited, and from the viewpoint of improving the manufacturability of the resin sheet, the ratio of the wetting dispersing agent to the inorganic filler (C) is preferably 0.1 to 5% by mass, preferably 0.5 to 3 by mass. % is better. Further, when two or more kinds of wetting and dispersing agents are used in combination, it is preferred that the total amount is in accordance with the above ratio.

Moreover, the insulating layer of the present invention may contain a curing accelerator for the purpose of adjusting the curing rate and the like. The hardening accelerator is known as a hardening accelerator such as an epoxy compound or a cyanate compound, and is not particularly limited as long as it is a general user. Specific examples thereof include organic metal salts (for example, zinc octoate, cobalt naphthenate, nickel octylate, manganese octylate, etc.) containing metals such as copper, zinc, cobalt, nickel, and manganese, and imidazoles and derivatives thereof (for example, 2- Ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole, etc.), tertiary amines (for example, triethylamine, tributylamine, etc.) and the like. These hardening accelerators may be used singly or in combination of two or more kinds in any combination and in any ratio.

When the hardening accelerator is used, the content thereof is not limited, but from the viewpoint of obtaining a high glass transition temperature, the ratio of the hardening accelerator is preferably 0.01 to 5 parts by mass, preferably 0.05 based on 100 parts by mass of the resin solid content of the insulating layer. ~4 parts by mass is better. Further, when two or more kinds of curing accelerators are used in combination, it is preferred that the total amount is in accordance with the above ratio.

Further, the insulating layer of the present invention may contain various other polymer compounds or flame retardant compounds, etc., within the range which does not impair the desired properties. The polymer compound and the flame retardant compound are not limited as long as they are general users. The polymer compound is, for example, various thermosetting resins, thermoplastic resins, oligomers thereof, and elastomers. a flame retardant compound such as a phosphorus-containing compound (for example, a phosphate ester, a melamine phosphate, a phosphorus-containing epoxy resin, etc.), a nitrogen-containing compound (for example, melamine, benzoguanamine, etc.), a compound of a ring, an anthrone-based compound, or the like. These polymer compounds or flame-retardant compounds may be used singly or in combination of two or more kinds in any combination and in any ratio.

Further, the insulating layer of the present invention may contain various additives for various purposes within the range which does not impair the desired characteristics. Additives such as: ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, tackifiers, lubricants, defoamers, dispersants, leveling agents, Gloss agent, etc. These additives may be used singly or in combination of two or more kinds in any combination and in any ratio.

[I-8. Varnish] The varnish may be prepared by dissolving or dispersing the above components (A) to (E) and other components as necessary in a solvent. This varnish is suitable for producing the resin sheet of the present invention to be described later. The solvent is not limited as long as it can dissolve or disperse the above components as desired, and does not impair the desired effects of the present invention. Specific examples thereof include alcohols (methanol, ethanol, propanol, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), guanamines (for example, dimethyl acetamide, dimethylformamide). Etc.), aromatic hydrocarbons (such as toluene, xylene, etc.). These organic solvents may be used singly or in combination of two or more kinds in any combination and in any 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 the printed circuit board is manufactured using the resin sheet, the outer layer may be peeled off or etched from the resin sheet as needed.

The outer layer is not particularly limited, and a polymer film, a metal foil or a metal film can be used. Specific examples of the polymer film include a material selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polybutene, polybutadiene, polyurethane, ethylene-oxyethylene copolymer, and poly(terephthalic acid). Polyesters such as ethylene glycol ester, polyethylene naphthalate and polybutylene terephthalate, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polyimine and a film of at least one or more resins of the group consisting of polyamines, and a release film coated with a release agent on the surface of the films, among which polyester, polyimide, and Polyamine is preferred, and polyethylene terephthalate which is a polyester is particularly preferred. 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 the metal film include a foil or a 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 suitable. A known surface treatment such as nickel treatment or cobalt treatment may be applied to the metal foil or the metal film. The thickness of the metal foil or the metal film may be appropriately adjusted depending on the intended use, and is, for example, preferably in the range of 5 to 70 μm.

The method of forming the insulating layer of the present invention on the above outer layer to produce the resin sheet of the present invention is not limited. For example, the varnish is applied to the surface of the outer layer, dried under heating or reduced pressure, and the solvent is removed to cure the varnish. The drying conditions are not particularly limited, and are usually dried so that the content ratio of the solvent is 10 parts by mass or less, preferably 5 parts by mass or less, based on the total amount of the insulating layer formed in such a manner. The conditions for achieving the drying vary depending on the amount of the organic solvent in the varnish. For example, when the varnish contains 30 to 60 parts by mass of the organic solvent, it can be dried under heating at 50 to 160 ° C for about 3 to 10 minutes. In the resin sheet of the present invention, the thickness of the insulating layer is not limited, but it is preferably from 0.1 to 500 μm from the viewpoint of more excellent removal of light volatile components during drying and from the viewpoint of functioning as a resin sheet more effectively and surely. The scope. In the case where the resin composition has fluidity without a solvent, the resin composition can be used as a varnish to form an insulating layer. Further, if the insulating layer formed of the varnish or the resin composition having fluidity is compared, and the method of forming it differently (melting and pressing the resin, etc.) is compared, the layer uniformity of the former or the outer layer is dense. The combination is superior.

The resin sheet of the present invention can be used as a deposition material for a printed circuit board. In the printed circuit board formed using the resin sheet of the present invention, the insulating layer of the present invention constitutes an insulating layer of the printed circuit board. The insulating layer of the printed circuit board is usually hardened. The printed circuit board is detailed below.

[II-2. Printed Circuit Board] The printed circuit board of the present invention can be obtained by using the resin sheet of the present invention as a stacked material for a core substrate. The core substrate is a substrate that becomes a core in the stacking 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 metal foil of a metal foil-clad laminate used in the technical field or a conductor layer obtained by peeling a metal foil and then plating or the like is usually used to form a conductor circuit. The nuclear substrate refers to a conductor layer in which pattern processing is formed on one or both sides of a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. (circuit). Further, an inner layer circuit substrate in which an intermediate layer of an insulating layer or a conductor layer is to be formed when manufacturing a multilayer printed circuit board is also included in the circuit substrate of the present invention. Further, when the surface of the conductor layer (circuit) is subjected to roughening treatment in advance by a blackening treatment or the like, it is preferable 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 hardened to constitute an insulating layer of a printed circuit board.

Specifically, when the resin sheet of the present invention is used as a deposition material, the surface of the insulating layer of the resin sheet is subjected to a surface treatment by a usual method, and a wiring pattern (conductor layer) is formed by plating on the surface of the insulating layer. The printed circuit board of the present invention. Other various steps (for example, a hole processing such as forming a via hole, a through hole, or the like) may be applied as needed. The following is a description of the various steps for manufacturing the printed circuit board of the present invention.

1) Surface treatment The surface treatment of the insulating layer is carried out in consideration of the viewpoint of improving the adhesion between the insulating layer and the plated conductor layer, and the stain removal. The surface treatment includes a stain removal treatment, a decane coupling treatment, and the like. The stain removal treatment preferably includes swelling, surface roughening and stain dissolution, and neutralization treatment. The roughening treatment is 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 kinds of acrylonitrile-butadiene rubbers having different molecular weights are used, and by subjecting the insulating layer containing the rubber to surface treatment in such a manner, the chipping marks can be reduced and a low surface roughness can be achieved.

The roughening treatment is preferably to remove the stain generated in the opening step. In this case, since the degree of hardening of the insulating layer is different, the roughening state may be different. Therefore, it is preferable to select the optimum conditions for the combination of the subsequent forming conditions and the subsequent roughening treatment conditions and plating conditions. In an ideal aspect, the roughening treatment first uses a swelling agent to swell the surface insulating layer. The swelling agent is not limited as long as it can improve the moisture permeability of the surface insulating layer and swell the surface insulating layer to such an extent that it can promote the subsequent surface roughening and oxidative decomposition of the stain-dissolving treatment. For example, an alkali solution, a surfactant solution, and the like. Next, the swollen surface is treated with an oxidizing agent to oxidatively decompose and roughen the surface. At this time, the stain generated by the process is also removed. The oxidizing agent, for example, an alkaline permanganate solution or the like, is preferably a potassium permanganate aqueous solution or a sodium permanganate aqueous solution. The oxidant treatment is called wet decontamination, and in addition to the wet decontamination, it is also possible to use a plasma treatment, a UV treatment for dry decontamination, a buffing, etc. for mechanical grinding, sanding, and the like. Other known roughening treatments are appropriately combined and implemented. Further, the oxidizing agent used in the pretreatment is neutralized with a reducing agent by a neutralization treatment. The reducing agent may, for example, be an amine-based reducing agent, and a specific example thereof may be an acidic aqueous solution such as a hydroxylamine sulfate aqueous solution, an ethylenediaminetetraacetic acid aqueous solution or a nitrogen-based triacetic acid aqueous solution.

In forming the fine wiring pattern, the surface unevenness of the insulating layer after the roughening treatment is preferably small. Specifically, Rz 値 is preferably 4.0 μm or less, more preferably 2.0 μm or less. The surface unevenness after the roughening treatment is determined depending on the degree of hardening of the insulating layer, the conditions of the roughening treatment, and the like, and it is preferable to select an optimum condition for obtaining the unevenness of the desired surface. In particular, the insulating layer of the present invention is highly desirable because it can ensure adhesion to the plated conductor layer even if the surface roughness is low.

2) Formation of Conductor Layer A method of forming a wiring pattern (conductor layer) by plating may be a semi-additive method, a full addition method, or a subtractive method. Among them, a semi-additive method is preferable in view of the viewpoint of forming a fine wiring pattern. As a method of forming a pattern by a semi-additive method, for example, after forming a thin conductor layer by electroless plating or the like on the surface of the insulating layer, electrolytic plating (pattern plating) is selectively applied using a plating resist, and then A method in which a plating resist is peeled off and an entire amount is etched to form a wiring pattern. As a method of forming a pattern by a full-addition method, for example, a method of forming a pattern by using a plating resist on a surface of an insulating layer and selectively attaching electroless plating or the like to form a wiring pattern is used. As a method of forming a pattern by subtraction, for example, after a conductor layer is formed by plating on the surface of an insulating layer, a conductor layer is selectively removed using an etching resist to form a wiring pattern. Alternatively, when the outer layer of the resin sheet is a metal foil or a metal film, these may be etched to form a wiring pattern.

When a wiring pattern is formed by plating, it is preferable to perform drying after plating in view of improving the adhesion strength between the insulating layer and the conductor layer. In the pattern formation by the semi-additive method, electroless plating is performed in combination with electrolytic plating. In this case, it is preferred to perform drying after electroless plating and electrolytic plating, respectively. The drying after electroless plating is preferably carried out, for example, at 80 to 180 ° C for 10 to 120 minutes, and the drying after electrolytic plating is preferably carried out at 130 to 220 ° C for 10 to 120 minutes. The electroless plating layer is superior in layer uniformity to the electrolytic plating layer, so that both can be distinguished.

3) Others In order to manufacture a printed circuit board, the resin sheet of the present invention can be subjected to a hole processing. This treatment is performed to form a through hole, a through hole, or the like. For the hole processing, any one of known methods such as an NC drill, a carbon dioxide gas laser, a UV laser, a YAG laser, and a plasma may be used, or two or more types may be combined as needed.

The printed circuit board of the present invention can also be fabricated into a multilayer printed circuit board. For example, after forming a laminated board of the present invention which has been subjected to a plating treatment, an inner layer circuit is formed on the laminated board, and a blackening treatment is performed on the obtained circuit to form an inner layer circuit board. The resin sheet of the present invention is disposed on one or both sides of the inner layer circuit board thus obtained, and then a metal foil (for example, copper, aluminum, etc.) or a release film (in a polyethylene film, a polypropylene film, or a polycarbonate) is disposed on the outer side thereof. a film coated with a release agent such as an ester film, a polyethylene terephthalate film or an ethylene tetrafluoroethylene copolymer film, and repeating such an operation and laminating the film to form a multilayer printed circuit board .

The laminate molding system is generally used for laminating a laminate of a conventional printed circuit board, for example, multi-stage pressing, multi-stage vacuum pressing, laminator, vacuum laminator, autoclave molding machine, etc. at a temperature. For example, it is suitably selected and carried out in the range of, for example, 100 to 300 ° C, a pressure of, for example, 0.1 to 100 kgf/cm ² (about 9.8 kPa to about 38 MPa), and a heating time of, for example, 30 seconds to 5 hours. Further, post-hardening may be performed at a temperature of, for example, 150 to 300 ° C as needed, and the degree of hardening may be adjusted. [Examples]

The present invention will be described in detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

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

【化7】 (wherein n ⁷ is in the range of 3 to 4 in terms of average 。.)

The reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux cooler was previously cooled to 0 to 5 ° C with brine, and 7.27 g (0.122 mol) of cyanogen chloride and 9.75 g of 35% hydrochloric acid (0.0935) were charged therein. Mol), water 76 ml, and dichloromethane 44 ml.

The temperature in the reactor was maintained at -5 to +5 ° C, the pH was kept at 1 or less, and the α-naphthol aralkyl resin represented by the following formula (8) was added dropwise with stirring for 1 hour under stirring. SN485, OH group equivalent: 214g / eq. Softening point: 86 ° C, manufactured by Nippon Steel Chemical Co., Ltd.) 20g (0.0935mol), and triethylamine 14.16g (0.14mol) dissolved in 92ml of dichloromethane After the completion of the dropwise addition, a solution of 4.72 g (0.047 mol) of triethylamine was added dropwise over 15 minutes.

【化8】 (wherein n ⁸ is in the range of 3 to 4 in terms of average 。.)

After completion of the dropwise addition, the mixture was stirred at the same temperature for 15 minutes, and then the reaction liquid was separated, and the organic phase was separated. After the obtained organic phase was washed twice with 100 ml of water, the dichloromethane was distilled off under reduced pressure using an evaporator, and finally concentrated and dried at 80 ° C for 1 hour to obtain α-naphthol represented by the above formula (7). Cyanate ester of an aralkyl resin (α-naphthol aralkyl type cyanate compound) 23.5 g.

[Preparation of varnish and resin sheet] Example 1 A biphenyl aralkyl type epoxy compound as an epoxy compound (A) (NC-3000-FH, epoxy equivalent: 320 g/eq., Nippon Kayaku Co., Ltd.) 83.1 parts by mass of the MEK solution (nonvolatile content: 70% by mass), which is 58.2 parts by mass in terms of nonvolatile content, and α-naphthol aryl obtained as the cyanate compound (B) in Synthesis Example 1. a solution of a methyl ethyl ketone compound (cyanate equivalent: 261 g/eq.) in methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK") (nonvolatile content: 50% by mass) of 58 parts by mass (in terms of nonvolatile content) 29 parts by mass), a phenol varnish type maleic imine compound (BMI-2300, manufactured by KI Chemical Co., Ltd.) represented by the formula (5) as a maleic imine compound, 4.9 parts by mass, double Malay Ammonium compound (BMI-1000P, manufactured by KI Chemical Co., Ltd.) 4.9 parts by mass of DMAc solution (non-volatile content: 20% by mass) of 2,4,5-triphenylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing accelerator 15 parts by mass (3 parts by mass in terms of nonvolatile content) and 0.8 parts by mass of a zinc octoate (nonvolatile content: 10% by mass) (dissolved in a nonvolatile content: 0.08 parts by mass) dissolved or dispersed MEK. Then, an acrylonitrile-butadiene rubber (N215SL, JSR) having a weight average molecular weight of about 144,000 (measured by GPC manufactured by Agilent Technology Co., Ltd.) as a first acrylonitrile-butadiene rubber (D) was added. 7.5 parts by mass of the MEK solution (non-volatile component 20% by mass) of viscosity 45) (1.5 parts by mass in terms of nonvolatile content), and acrylonitrile-butadiene as the second acrylonitrile-butadiene rubber (E) Ethene rubber (N280, JSR (strand), weight average molecular weight: about 9,000 (measured by GPC by Agilent Technology)) MEK solution (non-volatile component 20% by mass) 7.5 parts by mass (1.5 in terms of nonvolatile content) Parts by mass). Further, 85.7 parts by mass of magnesium oxide MEK slurry (SMO-0.4, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter: 0.4 μm, nonvolatile component: 70% by mass) as an inorganic filler (C) was added. Conversion: 60 parts by mass), aniline decane treated cerium oxide MEK slurry (SC2050-MTX, manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm, nonvolatile component 70% by mass) 107.1 parts by mass (according to non-volatile The composition conversion is 75 parts by mass). After the addition, the mixture was stirred for 30 minutes using a high-speed stirring device to obtain an epoxy compound (A), a cyanate ester compound (B), an inorganic filler (C), a first acrylonitrile-butadiene rubber (D), and a second propylene. Varnish of nitrile-butadiene rubber (E). This varnish was applied to a polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) having a thickness of 38 μm coated with a release agent, and dried by heating at 100 ° C for 3 minutes. As the insulating layer, a resin sheet having a polyethylene terephthalate film on the outer layer was obtained.

【化9】 (wherein R ⁵ each independently represents a hydrogen atom or a methyl group. n ⁵ is in the range of 1 to 10 in terms of an average enthalpy.)

[Production of inner layer circuit board] A glass cloth substrate BT resin having a double layer copper-clad laminate (having a copper foil thickness of 18 μm, a substrate thickness of 0.2 mm, and a CCL-HL832NX type A manufactured by Mitsubishi Gas Chemical Co., Ltd.) On both sides, a copper surface roughening treatment was performed by etching 1 μm with a CZ8100 manufactured by Mec Co., Ltd. to obtain an inner layer circuit substrate.

[Production of printed circuit board] The insulating layer of the obtained resin sheet was placed on the inner layer circuit board, and vacuum suction was performed for 30 seconds (5.0 MPa or less) using a vacuum laminator (manufactured by Nichigo Morton) at a pressure of 10 kgf/ The laminate was formed by cm ² at a temperature of 100 ° C for 30 seconds. Further, lamination molding was carried out for 60 seconds at a pressure of 10 kgf/cm ² and a temperature of 100 ° C to obtain a printed circuit board. The obtained printed circuit board was dried at 180 ° C for 60 minutes to sufficiently harden it to obtain a printed circuit board.

Example 2 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 55.6 parts by mass (27.8 parts by mass in terms of nonvolatile content), and biphenyl The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 79.3 parts by mass (55.5 parts by mass in terms of nonvolatile content), and the double mala The amount of the imine compound (BMI-1000P) was changed to 4.6 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.6 parts by mass, and the first acrylonitrile-butadiene rubber (N215SL) The amount of the MEK solution (non-volatile content: 20% by mass) was changed to 19 parts by mass (3.8 parts by mass in terms of nonvolatile content) and the second acrylonitrile-butadiene rubber (N280) in MEK solution (non- A varnish was prepared in the same manner as in Example 1 except that the amount of the volatile component (20% by mass) was changed to 19 parts by mass (3.8 parts by mass in terms of a nonvolatile component), and a resin sheet and a printed circuit board using the resin sheet were obtained. .

Example 3 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 54 parts by mass (27 parts by mass in terms of nonvolatile matter), and biphenyl. The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content), and the double Malay The amount of the imine compound (BMI-1000P) was changed to 4.5 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.5 parts by mass, and the first acrylonitrile-butadiene rubber (N215SL) The use amount of the MEK solution (non-volatile content: 20% by mass) is changed to 25 parts by mass (5.0 parts by mass in terms of nonvolatile content), and the second acrylonitrile-butadiene rubber (N280) is used in MEK solution. A varnish was prepared in the same manner as in Example 1 except that the amount of the volatile component (20% by mass) was changed to 25 parts by mass (5.0 parts by mass in terms of a nonvolatile component), and a resin sheet and a printed circuit board using the resin sheet were obtained. .

Example 4 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 55.6 parts by mass (27.8 parts by mass in terms of nonvolatile content), and biphenyl. The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 79.3 parts by mass (55.5 parts by mass in terms of nonvolatile content), and the double mala The amount of the imine compound (BMI-1000P) was changed to 4.6 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.6 parts by mass, and the first acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content: 20% by mass) is changed to 9.5 parts by mass (1.9 parts by mass in terms of nonvolatile content), and MEK solution of liquid acrylonitrile-butadiene rubber (N280) (non- A varnish was prepared in the same manner as in Example 1 except that the amount of the volatile component (20% by mass) was changed to 28 parts by mass (5.6 parts by mass in terms of a nonvolatile component), and a resin sheet and a printed circuit board using the resin sheet were obtained. .

Example 5 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 54 parts by mass (27 parts by mass in terms of nonvolatile matter), and biphenyl. The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content), and the double Malay The amount of the imine compound (BMI-1000P) was changed to 4.5 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.5 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content: 20% by mass) is changed to 25 parts by mass (5.0 parts by mass in terms of nonvolatile content), and MEK solution of liquid acrylonitrile-butadiene rubber (N280) (non- The amount of the volatile component (20% by mass) was changed to 25 parts by mass (5.0 parts by mass in terms of nonvolatile content), and the anthracene decane treated cerium oxide MEK slurry (SC2050-MTX, nonvolatile matter 70% by mass) A varnish was prepared in the same manner as in Example 1 except that the amount of use was changed to 178.6 parts by mass (125 parts by mass in terms of nonvolatile content), and a tree was obtained. A fat sheet and a printed circuit board using the resin sheet.

Example 6 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 54 parts by mass (27 parts by mass in terms of nonvolatile matter), and biphenyl. The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content), and the double Malay The amount of the imine compound (BMI-1000P) was changed to 4.5 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.5 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content: 20% by mass) is changed to 25 parts by mass (5.0 parts by mass in terms of nonvolatile content), and MEK solution of liquid acrylonitrile-butadiene rubber (N280) (non- The amount of the volatile component (20% by mass) was changed to 25 parts by mass (5.0 parts by mass in terms of nonvolatile content), and the anthracene decane treated cerium oxide MEK slurry (SC2050-MTX, nonvolatile matter 70% by mass) A varnish was prepared in the same manner as in Example 1 except that the amount of use was changed to 285.7 parts by mass (200 parts by mass in terms of nonvolatile content), and a tree was obtained. A fat sheet and a printed circuit board using the resin sheet.

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

Comparative Example 2 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 56.8 parts by mass (28.4 parts by mass in terms of nonvolatile content), and biphenyl. The amount of the MEK solution (non-volatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 81.4 parts by mass (57.0 parts by mass in terms of nonvolatile content), and the double horse was used. The amount of the imine compound (BMI-1000P) was changed to 4.8 parts by mass, and the amount of the novolak maleic imide compound (BMI-2300) was changed to 4.8 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content 20% by mass) is changed to 25 parts by mass (5 parts by mass in terms of nonvolatile content), and MEK solution of liquid acrylonitrile-butadiene rubber (N280) (non- A varnish was prepared in the same manner as in Example 1 except that the amount of the volatile component (20% by mass) was changed to 0 parts by mass, and a resin sheet and a printed circuit board using the resin sheet were obtained.

Comparative Example 3 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 54 parts by mass (27 parts by mass in terms of nonvolatile content), and biphenyl. The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content), and the double Malay The amount of the imine compound (BMI-1000P) was changed to 4.5 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.5 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content: 20% by mass) is changed to 50 parts by mass (10 parts by mass in terms of nonvolatile content), and MEK solution of liquid acrylonitrile-butadiene rubber (N280) (non- A varnish was prepared in the same manner as in Example 1 except that the amount of the volatile component (20% by mass) was changed to 0 parts by mass, and a resin sheet and a printed circuit board using the resin sheet were obtained.

Comparative Example 4 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 51.0 parts by mass (25.5 parts by mass in terms of nonvolatile content), and biphenyl. The amount of the MEK solution (non-volatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 72.9 parts by mass (51.0 parts by mass in terms of nonvolatile content), and the double horse was used. The amount of the imine compound (BMI-1000P) was changed to 4.3 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.3 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content 20% by mass) is changed to 75 parts by mass (15 parts by mass in terms of nonvolatile content), and MEK solution of liquid acrylonitrile-butadiene rubber (N280) (non- A varnish was prepared in the same manner as in Example 1 except that the amount of the volatile component (20% by mass) was changed to 0 parts by mass, and a resin sheet and a printed circuit board using the resin sheet were obtained.

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

Comparative Example 6 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 56.8 parts by mass (28.4 parts by mass in terms of nonvolatile content), and biphenyl The amount of the MEK solution (non-volatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 81.4 parts by mass (57.0 parts by mass in terms of nonvolatile content), and the double horse was used. The amount of the imine compound (BMI-1000P) was changed to 4.8 parts by mass, and the amount of the novolak maleic imide compound (BMI-2300) was changed to 4.8 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content: 20% by mass) was changed to 0 parts by mass, and the amount of MEK solution (non-volatile content: 20% by mass) of liquid acrylonitrile-butadiene rubber (N280) was changed to 25 A varnish was prepared in the same manner as in Example 1 except that a mass fraction (5 parts by mass in terms of a nonvolatile component) was obtained, and a resin sheet and a printed circuit board using the resin sheet were obtained.

Comparative Example 7 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 54 parts by mass (27 parts by mass in terms of nonvolatile content), and biphenyl. The amount of the MEK solution (nonvolatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 77.1 parts by mass (54.0 parts by mass in terms of nonvolatile content), and the double Malay The amount of the imine compound (BMI-1000P) was changed to 4.5 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.5 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content of 20% by mass) was changed to 0 parts by mass, and the amount of MEK solution (non-volatile content of 20% by mass) of liquid acrylonitrile-butadiene rubber (N280) was changed to 50. A varnish was prepared in the same manner as in Example 1 except that a mass fraction (10 parts by mass in terms of a nonvolatile component) was obtained, and a resin sheet and a printed circuit board using the resin sheet were obtained.

Comparative Example 8 The amount of the MEK solution (nonvolatile content: 50% by mass) of the α-naphthol aralkyl type cyanate compound was changed to 51.0 parts by mass (25.5 parts by mass in terms of nonvolatile content), and biphenyl. The amount of the MEK solution (non-volatile content: 70% by mass) of the aralkyl type epoxy compound (NC-3000-FH) was changed to 72.9 parts by mass (51.0 parts by mass in terms of nonvolatile content), and the double horse was used. The amount of the imine compound (BMI-1000P) was changed to 4.3 parts by mass, and the amount of the novolac maleic imide compound (BMI-2300) was changed to 4.3 parts by mass, and the solid acrylonitrile-butadiene rubber (N215SL) The amount of MEK solution (non-volatile content of 20% by mass) was changed to 0 parts by mass, and the amount of MEK solution (non-volatile content of 20% by mass) of liquid acrylonitrile-butadiene rubber (N280) was changed to 75. A varnish was prepared in the same manner as in Example 1 except that a mass fraction (15 parts by mass in terms of a nonvolatile component) was obtained, and a resin sheet and a printed circuit board using the resin sheet were obtained.

[Evaluation of Resin Sheets] (1) Flexibility The resin sheets prepared according to the procedures of Examples 1 to 6 and Comparative Examples 1 to 8 were used, and in order to confirm the handleability of the resin sheets, samples of the obtained resin sheets of 100 mm × 100 mm were obtained. Bend 180° to visually observe whether cracks have occurred. Those who did not have cracks were rated as "a". Then, for the occurrence of cracking, whether or not cracking occurred when the resin sheet was wound around a rod of φ15 mm was visually observed. Those who did not have a crack were rated as "b". Those who have cracked in all the above evaluations are rated as "c". The results are shown in Table 1.

[Evaluation of Printed Circuit Board] Wet Roughening Treatment of Printed Circuit Board and Conductive Layer Plating The outer layer was peeled off from the printed circuit boards obtained in Examples 1 to 6 and Comparative Examples 1 to 8. For the exposed insulating layer, the electroless copper plating treatment by Uemura Industrial Co., Ltd. (using liquid chemical name: MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver. 2) is used. Electroless copper plating of about 0.8 μm was applied and dried at 130 ° C for 1 hour. Then, electrolytic copper plating was applied to make the thickness of the plated copper 18 μm, and it was dried at 180 ° C for 1 hour. In this manner, a sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was prepared for the following evaluation.

(2) Plating copper adhesion Using the sample prepared according to the above procedure, the adhesion of the plated copper was measured 3 times in accordance with JIS C6481, and the average enthalpy was determined. For the sample which was raised due to the drying after electrolytic copper plating, the portion which was not raised was used for evaluation. The results are shown in Table 1.

(3) Surface roughness The surface of the sample prepared by the above procedure was plated with copper, and the surface of the insulating layer was determined from a 3000-fold image using a laser microscope (VK-9500, Keyence) (10-point average). Roughness) and Ra (arithmetic mean roughness). The results are shown in Table 1.

(4) Maximum collapse size The sample prepared according to the above procedure has been roughened in the electroless plating step, and the acrylonitrile-butadiene rubber is formed by the erosion of the rough surface liquid. . Using SEM-EDX (JSM-6460LA manufactured by JEOL), the diameter of the chipping mark was selected from the image of 1000 times and the image of 10000 times, and the maximum collapse size was determined. The results are shown in Table 1.

(5) Glass transition temperature (Tg) A resin sheet having an insulating layer thickness of 0.05 mm which was cured at 180 ° C for 2 hours was heated at a temperature of 10 ° C per minute from 25 ° C to 250 ° C using a thermomechanical analyzer (Q800 manufactured by TA Instrument). , the glass transition temperature was measured. The results are shown in Table 1.

【Table 1】 [Industry Utilization]

When the resin sheet of the present invention is used as a material of the insulating layer of the printed circuit board, it can exhibit various effects such as excellent handleability of the resin sheet and excellent adhesion between the insulating layer and the plated conductor layer. The material of the insulating layer of the printed circuit board is extremely useful.

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Claims (12)

A resin sheet comprising: an outer layer 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 containing an epoxy compound ( A), a cyanate ester compound (B), an inorganic filler (C), a first acrylonitrile-butadiene rubber (D) having a weight average molecular weight of 100,000 or more as measured by GPC, and a weight average molecular weight of 1,000 Å. 30,000 of the 2nd acrylonitrile-butadiene rubber (E). The resin sheet of the first aspect of the invention, wherein the content X of the first acrylonitrile-butadiene rubber (D) is 0 < X < 15 parts by mass based on 100 parts by mass of the resin solid content. The resin sheet of the first or second aspect of the invention, wherein the content Y of the second acrylonitrile-butadiene rubber (E) is 0 < Y < 15 parts by mass based on 100 parts by mass of the resin solid content. The resin sheet of claim 1 or 2, wherein the content of the first acrylonitrile-butadiene rubber (D) X and the content of the second acrylonitrile-butadiene rubber (E) Y are X+Y It is 0 < X + Y < 15 parts by mass with respect to 100 parts by mass of the resin solid content. The resin sheet of claim 1 or 2, wherein the insulating layer further contains a maleic imine compound (F). The resin sheet according to claim 1 or 2, wherein the polymer film is selected from the group consisting of polyester, polyimine, and polyamine. The resin sheet according to claim 1 or 2, wherein the insulating layer is coated on the outer layer of the resin composition containing the components (A) to (E), and dried and cured under heating or reduced pressure. And got it. A printed circuit board comprising an insulating layer according to any one of claims 1 to 7 which is laminated on a circuit substrate having a core substrate and a conductor circuit formed on the core substrate. The printed circuit board of claim 8, wherein the insulating layer is surface-treated and has a patterned conductor layer on the surface. The printed circuit board of claim 9, wherein the surface treatment is a stain removal treatment comprising a roughening treatment using a swelling agent and an alkali oxidizing agent, and a neutralization treatment using an acidic reducing agent. The printed circuit board of claim 9 or 10, wherein the conductor layer comprises a conductor layer formed by a semi-additive method or a conductor layer formed by subtraction. The printed circuit board of claim 9 or 10, wherein the conductor layer comprises a conductor layer obtained by etching a layer formed of a metal foil or a metal film as in the first aspect of the patent application.