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WO2016088744A1 - Feuille de résine, et carte de circuit imprimé - Google Patents

Feuille de résine, et carte de circuit imprimé Download PDF

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Publication number
WO2016088744A1
WO2016088744A1 PCT/JP2015/083715 JP2015083715W WO2016088744A1 WO 2016088744 A1 WO2016088744 A1 WO 2016088744A1 JP 2015083715 W JP2015083715 W JP 2015083715W WO 2016088744 A1 WO2016088744 A1 WO 2016088744A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
parts
insulating layer
resin sheet
acrylonitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/083715
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English (en)
Japanese (ja)
Inventor
秀和 出井
誠司 四家
恵一 長谷部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP2016562629A priority Critical patent/JP6638887B2/ja
Publication of WO2016088744A1 publication Critical patent/WO2016088744A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • 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.
  • Patent Document 1 discloses a technique of adding liquid rubber for improving crack resistance from the viewpoint of improving handling properties.
  • 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.
  • Patent Document 1 can improve crack resistance, but does not describe any concept of high glass transition temperature.
  • Patent Document 2 is excellent in adhesiveness and fluidity, the document does not describe the flexibility of the semi-cured resin sheet at all.
  • 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.
  • 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.
  • 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.
  • a second acrylonitrile-butadiene rubber (E) having a weight average molecular weight of 1,000 to 30,000.
  • 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.
  • [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.
  • the conductor layer includes a conductor layer formed by a semi-additive method or a conductor layer formed by a subtractive method.
  • 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).
  • the resin sheet is excellent in flexibility (handling property).
  • (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).
  • X to Y includes X and Y which are their end values.
  • X or Y means either X or Y or both.
  • 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”.
  • the insulating layer may contain a solvent.
  • 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”.
  • each component will be described.
  • 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).
  • 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.
  • 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
  • a bisnaphthalene type epoxy an epoxy group-containing compound having a naphthalene skeleton: a naphthalene bifunctional epoxy compound
  • 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.
  • 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 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).
  • the combustion resistance of the insulating layer can be improved.
  • 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.
  • the “resin solid content of the insulating layer” is a component excluding the inorganic filler (C) in the insulating layer.
  • the insulating layer may contain a solvent.
  • 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.
  • 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).
  • 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.
  • 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 C
  • 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. .
  • 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”.
  • 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.
  • 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.
  • aromatic hydrocarbon formaldehyde resin obtained by polymerizing aromatic hydrocarbon such as benzene, toluene, xylene and the like with formaldehyde
  • phenol Hydroxyl group-containing aromatic
  • a compound represented by the formula (2) is preferable.
  • 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.
  • novolac-type cyanate ester compound a compound represented by the formula (3) or the formula (4) is preferable.
  • 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.
  • 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.
  • 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”.
  • 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.
  • silica for example, natural silica, fused silica, amorphous si
  • 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.
  • silica is preferable as the inorganic filler (C), and among them, fused silica is particularly preferable.
  • 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.
  • 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.
  • magnesium hydroxide examples 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 ⁇ m and more preferably 0.2 to 2.0 ⁇ m from the viewpoint of improving the productivity of the resin sheet.
  • the “average particle diameter” of the inorganic filler (C) means the median diameter of the inorganic filler (C).
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the insulating layer of the present invention includes acrylonitrile-butadiene rubber having a bimodal molecular weight distribution.
  • excellent flexibility and low surface roughness can be imparted to the resin sheet.
  • this reason is not limited, it is guessed as follows.
  • 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.
  • the low molecular weight component (E) makes it possible to moderately suppress the aggregation of (D).
  • 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.
  • 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.
  • 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.
  • a long-chain alkyl bismaleimide represented by the formula (6) is preferable to use.
  • Commercially available products can be used as the compound, and examples thereof include BMI-1000P manufactured by KAI Kasei Co., Ltd.
  • n 6 represents an integer of 1 to 30
  • 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.
  • the amount of bismaleimide is in the range of 5 to 50 parts by mass, good moisture absorption heat resistance can be obtained.
  • the insulating layer of the present invention may contain a silane coupling agent for the purpose of improving moisture absorption heat resistance.
  • 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.
  • aminosilane-based silane coupling agents for example, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane
  • epoxysilane-based silane coupling agents for example, ⁇ -Glycidoxypropyltrimethoxysilane, etc.
  • vinylsilane-based silane coupling agents eg, ⁇ -methacryloxypropyltrimethoxysilane
  • cationic silane-based silane coupling agents eg, N- ⁇ - (N-vinylbenzyl) Aminoethyl) - ⁇ -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.
  • the silane coupling agent 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
  • 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.
  • the wetting dispersant 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
  • the insulating layer of the present invention may contain a curing accelerator for the purpose of adjusting the curing speed.
  • 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.
  • 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.
  • the curing accelerator 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
  • 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.
  • the polymer compound include various thermosetting resins and thermoplastic resins, oligomers thereof, and elastomers.
  • 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.
  • the insulating layer of the present invention may contain various additives for various purposes within a range where the intended characteristics are not impaired.
  • 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.
  • a 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.
  • the resin sheet of the present invention has the above-described insulating layer of the present invention on the outer layer.
  • the outer layer is not particularly limited, and a polymer film, metal foil, or metal film can be used.
  • 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.
  • polyester, polyimide, and polyamide are particularly preferable, and among them, polyethylene terephthalate, which is a kind of polyester, is particularly preferable.
  • the thickness of the polymer film is not particularly limited, and may be, for example, 0.002 to 0.1 mm.
  • 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 ⁇ m, 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.
  • 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.
  • 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 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the resin sheet of the present invention 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.
  • 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.
  • two acrylonitrile-butadiene rubbers having different molecular weights are used.
  • the roughening treatment also serves to remove smear generated by the drilling process.
  • 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.
  • 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.
  • the swollen surface is treated with an oxidizing agent, and the surface is oxidatively decomposed and roughened.
  • oxidizing agent examples 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.
  • reducing agent examples 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.
  • the surface roughness of the insulating layer after the roughening treatment is preferably small.
  • the Rz value is preferably 4.0 ⁇ m or less, more preferably 2.0 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a metal foil for example, copper or aluminum
  • 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.
  • 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 ⁇ -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.
  • n 8 is in the range from 3 to 4 as an average value.
  • 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 ⁇ -naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261 g / eq.) Obtained in Synthesis Example 1.
  • a MEK solution nonvolatile content 70% by mass
  • NC-3000-FH epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd.
  • B methyl ethyl ketone
  • 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.
  • BMI novolac maleimide
  • 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 ⁇ m, 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 ⁇ m, nonvolatile component 70% by mass) 107.1 parts by mass (in terms of nonvolatile content) 75 parts by mass) was added.
  • SMO-0.4 magnesium oxide MEK slurry
  • SC2050-MTX phenylaminosilane-treated silica MEK slurry
  • 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 ⁇ m 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.
  • TR1-38 polyethylene terephthalate film
  • a resin sheet having a terephthalate film as an outer layer was obtained.
  • 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.
  • 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 ⁇ -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.
  • MEK solution nonvolatile content 70% by mass
  • BMI-1000P bismaleimide compound
  • 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 ⁇ -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).
  • Example 4 The amount of ⁇ -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.
  • NC-3000- FH biphenyl aralkyl-type epoxy compound
  • BMI-1000P bismaleimide compound
  • Example 5 The amount of MEK solution of ⁇ -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).
  • Example 2 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 ⁇ -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).
  • Example 2 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.
  • N215SL solid acrylonitrile-butadiene rubber
  • N280 liquid acrylonitrile-butadiene rubber
  • 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.
  • N215SL solid acrylonitrile-butadiene rubber
  • N280 liquid acrylonitrile-butadiene rubber
  • 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.
  • 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
  • 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.
  • 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 ⁇ m 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 ⁇ m, 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 ⁇ m was formed on the insulating layer was prepared and subjected to the following evaluation.
  • the resin sheet of the present invention when 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.

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Abstract

L'invention fournit une feuille de résine qui peut être mise en œuvre dans une couche isolante à l'intérieur d'un matériau de carte de circuit imprimé, et qui contient une composition de résine se révélant excellente en termes de propriétés de manipulation lorsqu'elle prend la forme d'une feuille de résine, et également en termes d'adhérence entre une couche isolante et une couche de conducteur formée par placage à la surface de cette dernière. Cette feuille de résine contient : une couche externe d'une sorte choisie dans un groupe constitué d'un film polymère, d'une feuille métallique et d'un film métallique ; et une couche isolante stratifiée sur la couche externe. La couche isolante comprend un composé époxy (A), un composé ester de cyanate (B), une charge inorganique (C), un premier caoutchouc acrylonitrile-butadiène (D) dont la masse moléculaire moyenne en poids mesurée par chromatographie d'exclusion diffusion est supérieure ou égale à 100000, et un second caoutchouc acrylonitrile-butadiène (E) dont ladite masse moléculaire moyenne en poids est comprise entre 1000 et 30000.
PCT/JP2015/083715 2014-12-01 2015-12-01 Feuille de résine, et carte de circuit imprimé Ceased WO2016088744A1 (fr)

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WO2018003314A1 (fr) * 2016-06-29 2018-01-04 三菱瓦斯化学株式会社 Composition de résine, feuille de résine, carte de circuit imprimé multicouche et dispositif semi-conducteur
KR20190022517A (ko) * 2016-06-29 2019-03-06 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 수지 시트, 다층 프린트 배선판 및 반도체 장치

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JP7262918B2 (ja) * 2017-06-08 2023-04-24 日本発條株式会社 回路基板用積層板、金属ベース回路基板及びパワーモジュール
JP6909171B2 (ja) * 2018-02-12 2021-07-28 株式会社巴川製紙所 半導体装置製造用接着シート及びそれを用いた半導体装置の製造方法
JP6999459B2 (ja) * 2018-03-22 2022-01-18 太陽インキ製造株式会社 ドライフィルム、硬化物、および、電子部品

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KR102324899B1 (ko) 2016-06-29 2021-11-10 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 수지 시트, 다층 프린트 배선판 및 반도체 장치
CN109415491B (zh) * 2016-06-29 2022-05-03 三菱瓦斯化学株式会社 树脂组合物、树脂片材、多层印刷线路板以及半导体装置

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