WO2021020563A1 - Matériau de résine et carte de circuit imprimé multicouche - Google Patents

Matériau de résine et carte de circuit imprimé multicouche Download PDF

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Publication number
WO2021020563A1
WO2021020563A1 PCT/JP2020/029443 JP2020029443W WO2021020563A1 WO 2021020563 A1 WO2021020563 A1 WO 2021020563A1 JP 2020029443 W JP2020029443 W JP 2020029443W WO 2021020563 A1 WO2021020563 A1 WO 2021020563A1
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Prior art keywords
compound
resin material
material according
skeleton
formula
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PCT/JP2020/029443
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English (en)
Japanese (ja)
Inventor
悠子 川原
顕紀子 久保
達史 林
幸平 竹田
誠実 新土
悠太 大當
Original Assignee
積水化学工業株式会社
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Priority to CN202080055717.XA priority Critical patent/CN114206989B/zh
Priority to KR1020227002890A priority patent/KR20220043123A/ko
Priority to JP2020553561A priority patent/JPWO2021020563A1/ja
Publication of WO2021020563A1 publication Critical patent/WO2021020563A1/fr

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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 material containing a compound having an imide skeleton.
  • the present invention also relates to a multilayer printed wiring board using the above resin material.
  • a resin material is used to form an insulating layer for insulating the inner layers and to form an insulating layer located on a surface layer portion.
  • Wiring which is generally a metal, is laminated on the surface of the insulating layer.
  • a resin film obtained by forming the resin material into a film may be used. The resin material and the resin film are used as an insulating material for a multilayer printed wiring board including a build-up film.
  • Patent Document 1 discloses a resin composition containing a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group. .. Patent Document 1 describes that a cured product of this resin composition can be used as an insulating layer for a multilayer printed wiring board or the like.
  • Patent Document 2 includes (A) an epoxy resin and (B) a maleimide compound, and the component (B) is an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.
  • a resin composition containing at least one of the above is disclosed.
  • Patent Document 3 discloses a resin composition for an electronic material containing a bismaleimide compound, wherein the bismaleimide compound has two maleimide groups and one or more polyimide groups having a specific structure. .. In the bismaleimide compound, the two maleimide groups are independently bonded to both ends of the polyimide group via at least a first linking group in which 8 or more atoms are linearly linked. ..
  • Patent Document 4 describes a thermosetting resin composition used for forming an insulating layer in a printed wiring substrate, which contains a maleimide compound (A), and the maleimide compound (A) has a specific structure.
  • a resin composition for a printed wiring substrate containing at least the bismaleimide compound (A1) having the same is disclosed.
  • the thermal dimensional stability of the cured product may not be sufficiently high. Further, when the insulating layer is formed by using the conventional resin material as described in Patent Document 2, the dielectric loss tangent of the cured product may not be sufficiently lowered. As described in Patent Documents 3 and 4, when a resin material containing a maleimide compound having a specific structure is used, dielectric loss tangent and thermal dimensional stability can be improved to some extent, but further improvement is desired.
  • smear in the via may not be sufficiently removed by the desmear treatment at the time of forming the insulating layer.
  • the surface roughness after etching varies, and the plating peel strength with the metal layer laminated on the surface of the insulating layer by plating treatment is sufficiently high. It may not be.
  • the object of the present invention is that 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) smear can be effectively removed by the desmear treatment. 4) To provide a resin material capable of suppressing variation in surface roughness after etching and 5) increasing plating peel strength. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.
  • a resin material containing a compound having a structure represented by the following formula (X) and a curing accelerator is provided.
  • R represents an organic group and n represents a number of 1 or more.
  • n represents a number of 2 or more in the above formula (X).
  • R is a group having an aliphatic ring.
  • R has a partial skeleton of a skeleton derived from a dimer diamine.
  • R has a partial skeleton of a skeleton derived from a diamine compound other than a dimer diamine.
  • the nitrogen atom constituting the imide skeleton is bonded only to the carbon atom constituting the aliphatic skeleton.
  • the compound is a compound having a maleimide skeleton.
  • the compound is a compound having a maleimide skeleton at both ends.
  • the weight average molecular weight of the compound is 1000 or more and 100,000 or less.
  • the compound has a structure represented by the following formula (Y), the number of repetitions of the structure represented by the formula (X), and the following formula (Y). ) Is 100% of the total, and the number of repetitions of the structure represented by the formula (X) is 10% or more and 90% or less.
  • R1 represents a tetravalent organic group
  • R2 represents an organic group
  • m represents a number of 1 or more.
  • R1 does not have a phthalimide-derived skeleton
  • R2 does not have a phthalimide-derived skeleton. ..
  • R1 does not have an aromatic skeleton in the above formula (Y).
  • thermosetting compound contains an epoxy compound.
  • the curing agent comprises an active ester compound.
  • At least one of the epoxy compound and the active ester compound has an imide skeleton or an amide skeleton.
  • thermosetting compound comprises a radical curable compound.
  • the resin material includes an inorganic filler.
  • the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material.
  • the inorganic filler is silica.
  • the resin material is a resin film.
  • the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.
  • the plurality of insulating layers include a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers.
  • a multilayer printed wiring board is provided in which at least one of the layers is a cured product of the resin material described above.
  • the resin material according to the present invention contains a compound having a structure represented by the formula (X) and a curing accelerator. Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) desmear. Smear can be effectively removed by the treatment, 4) variation in surface roughness after etching can be suppressed, and 5) plating peel strength can be increased.
  • FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to an embodiment of the present invention.
  • the resin material according to the present invention includes a compound having a structure represented by the following formula (X) (hereinafter, may be referred to as compound X) and a curing accelerator.
  • R represents an organic group and n represents a number of 1 or more.
  • the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) desmear. Smear can be effectively removed by the treatment, 4) variation in surface roughness after etching can be suppressed, and 5) plating peel strength can be increased. With the resin material according to the present invention, all the effects of 1) -5) can be exhibited.
  • the resin material according to the present invention has the above-mentioned structure, the compatibility of the resin material can be enhanced. Further, since the resin material according to the present invention has the above-mentioned structure, the elongation characteristics of the cured product of the resin material can be improved.
  • the resin material according to the present invention may be a resin composition or a resin film.
  • the resin composition has fluidity.
  • the resin composition may be in the form of a paste.
  • the paste form contains a liquid.
  • the resin material according to the present invention is preferably a resin film because it is excellent in handleability.
  • the resin material according to the present invention is preferably a thermosetting resin material.
  • the resin film is preferably a thermosetting resin film.
  • the resin material according to the present invention contains compound X having a structure represented by the following formula (X).
  • the structure represented by the following formula (X) has a skeleton derived from 3,3', 4,4'-biphenyltetracarboxylic dianhydride.
  • the structure represented by the following formula (X) has an imide skeleton. Therefore, compound X has an imide skeleton.
  • Compound X is preferably a thermosetting compound. Only one compound X may be used, or two or more compounds may be used in combination.
  • preferable structures and the like capable of exerting the effects of the present invention more effectively will be specifically described.
  • R represents an organic group and n represents a number of 1 or more.
  • n preferably represents a number of 2 or more, preferably represents a number of 20 or less, and more preferably represents a number of 10 or less.
  • R includes a group having an aliphatic ring and the like.
  • the group having an aliphatic ring include a group having a cyclohexane ring, a group forming a part of a skeleton derived from a dimer diamine, and the like.
  • R is preferably a group having an aliphatic ring, and more preferably a group having a cyclohexane ring.
  • the cyclohexane ring means an alicyclic structure of a 6-membered ring in which 6 carbon atoms are cyclically bonded.
  • the carbon atom constituting the cyclohexane ring may be bonded to a hydrocarbon group having 1 or more and 20 or less carbon atoms, or may be bonded to a hydrocarbon group having 1 or more and 4 or less carbon atoms.
  • the compound X may have a cyclohexane ring as a ring constituting a tricyclodecane ring, a norbornane ring, an adamantane skeleton or the like.
  • the compound X may have a structure in which a plurality of cyclohexane rings are connected via a hydrocarbon group such as an alkyl group.
  • R in the above formula (X) is a group having a cyclohexane ring, the carbon atom constituting the cyclohexane ring and the skeleton derived from 3,3', 4,4'-biphenyltetracarboxylic dianhydride. It is preferable that the nitrogen atom in the above is directly bonded or is bonded via three or less atoms.
  • the atom is preferably a carbon atom.
  • R in the above formula (X) has the above tricyclodecane ring as a cyclohexane ring
  • the carbon atom constituting the tricyclodecane ring and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are used.
  • the nitrogen atom in the skeleton derived from the substance is directly bonded or is bonded via two or less atoms.
  • the atom is preferably a carbon atom.
  • R is the following formula (A1), the following formula (A2), the following formula (A3), the following formula (A4).
  • the following formula (A5), the following formula (A6), or the following formula (A7) is preferable.
  • R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms.
  • R1 to R10 are preferably hydrogen atoms or methyl groups, respectively.
  • R1 to R10 may be the same or different.
  • the group represented by the above formula (A1) has a cyclohexane ring.
  • R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms.
  • R1 to R10 are preferably hydrogen atoms or methyl groups, respectively.
  • R1 to R10 may be the same or different.
  • the group represented by the above formula (A2) has a cyclohexane ring.
  • the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring and 3,3', 4, 4
  • the nitrogen atom in the skeleton derived from'-biphenyltetracarboxylic dianhydride is directly bonded.
  • the second carbon atom (the carbon atom on the right side) constituting the cyclohexane ring and 3,3', 4, 4
  • a nitrogen atom in the skeleton derived from'-biphenyltetracarboxylic dianhydride is bonded via one carbon atom.
  • R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms.
  • R1 to R10 are preferably hydrogen atoms or methyl groups, respectively.
  • R1 to R10 may be the same or different.
  • the group represented by the above formula (A3) has a cyclohexane ring.
  • the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring and 3,3', 4, 4
  • a nitrogen atom in the skeleton derived from'-biphenyltetracarboxylic dianhydride is bonded via two carbon atoms.
  • the second carbon atom (carbon atom on the right side) constituting the cyclohexane ring and 3,3', 4, 4
  • the nitrogen atom in the skeleton derived from'-biphenyltetracarboxylic dianhydride is directly bonded.
  • R1 to R18 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and Q represents an arbitrary group.
  • R1 to R18 are preferably hydrogen atoms or methyl groups, respectively.
  • Q is preferably a hydrocarbon group having 1 to 4 carbon atoms or a group having an aromatic ring, more preferably an alkylene group, and even more preferably a methylene group. ..
  • Q when Q is a group having an aromatic ring, Q may be a group in which aromatic rings are bonded to each other via an ester bond.
  • R1 to R18 may be the same or different.
  • the group represented by the above formula (A4) has a cyclohexane ring.
  • the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring and 3,3', 4,4
  • the nitrogen atom in the skeleton derived from'-biphenyltetracarboxylic dianhydride is directly bonded.
  • the second carbon atom (carbon atom on the right side) constituting the cyclohexane ring and 3,3', 4,4
  • the nitrogen atom in the skeleton derived from'-biphenyltetracarboxylic dianhydride is directly bonded.
  • R1 to R8 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms.
  • R1 to R8 are preferably hydrogen atoms or methyl groups, respectively.
  • R1 to R8 may be the same or different.
  • R may be a group represented by the following formula (A5-1).
  • R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and two of R1 to R10 have a nitrogen atom constituting an imide skeleton. Represents a group that is bound.
  • R9 and R10 represent a group bonded to a nitrogen atom constituting an imide skeleton corresponds to the above formula (A5).
  • the groups represented by the above formula (A5) and the above formula (A5-1) have a norbornane ring.
  • R1 to R12 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms.
  • R1 to R12 are preferably hydrogen atoms or methyl groups, respectively.
  • R1 to R12 may be the same or different.
  • R may be a group represented by the following formula (A6-1).
  • R1 to R14 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and two of R1 to R14 have a nitrogen atom constituting an imide skeleton. Represents a group that is bound.
  • R13 and R14 represent a group bonded to a nitrogen atom constituting an imide skeleton corresponds to the above formula (A6).
  • the groups represented by the above formula (A6) and the above formula (A6-1) have a tricyclodecane ring.
  • the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring and Nitrogen atoms in the skeleton derived from 3,3', 4,4'-biphenyltetracarboxylic dianhydride are bonded via one carbon atom.
  • the second carbon atom (carbon atom on the right side) constituting the cyclohexane ring and Nitrogen atoms in the skeleton derived from 3,3', 4,4'-biphenyltetracarboxylic dianhydride are bonded via two carbon atoms.
  • the second carbon atom (the carbon atom on the right side) constituting the tricyclodecane ring And the nitrogen atom in the skeleton derived from 3,3', 4,4'-biphenyltetracarboxylic dianhydride are bonded via one carbon atom.
  • the group represented by the above formula (A7) has a cyclohexane ring.
  • the group represented by the above formula (A7) is a group derived from a dimer diamine.
  • a dimer diamine is used as a raw material.
  • the dimer diamine is a natural product (mixture)
  • the compound X preferably has a partial skeleton of a skeleton in which R is derived from a dimer diamine in the above formula (X), and other than the dimer diamine. It is also preferable to have a partial skeleton of the skeleton derived from the diamine compound.
  • the nitrogen atom constituting the imide skeleton is bonded only to the carbon atom constituting the aliphatic skeleton in the above formula (X). From the viewpoint of exerting the effects of the present invention even more effectively, it is preferable that the nitrogen atoms constituting the imide skeleton are bonded only to the carbon atoms constituting the aliphatic skeleton in the above-mentioned compound X.
  • the compound X is represented by the above formula (A5), the above formula (A6) or the above (A7) as R in the above formula (X). It is preferable to have a group represented by the above formula (A6) or the above formula (A7).
  • the compound X is represented by the above formula (A5) or the above formula (A6) as R in the above formula (X). It is preferable to have a group.
  • the compound X having a group represented by the above formula (A5) or the above formula (A6) has a shorter distance between the imide skeletons than the compound X having a group represented by the above formula (A7), and thus is a molecule. This is because it is possible to increase the concentration of the imide skeleton inside.
  • the compound X may have two types of structures represented by the above formula (X), may have two or more types, or may have three or more types.
  • the compound X may have a structure represented by the following formula (X1) as a structure represented by the above formula (X).
  • Two skeletons (skeleton A on the left side and skeleton B on the right side) having a structure represented by the following formula (X1) may be randomly arranged (for example, ... A / B / A / B ).
  • R1 and R2 each represent an organic group, and p and q each represent a number of 1 or more.
  • p and q each preferably represent a number of 2 or more, preferably a number of 10 or less, and more preferably a number of 7 or less.
  • the combination of R1 and R2 is preferably the following first combination, and more preferably the following second combination.
  • R1 is the above formula (A1), the above formula (A2), the above formula (A3), the above formula (A4), the above formula (A5), or the above formula (A6), and R2 is the above formula. (A7).
  • R1 is the above formula (A6) and R2 is the above formula (A7).
  • p preferably represents a number of 1 or more, more preferably represents a number of 3 or more, and a number of 18 or less. Is preferable, and it is more preferable to represent a number of 12 or less.
  • q more preferably represents a number of 1 or more, preferably represents a number of 10 or less, and represents a number of 8 or less. Is more preferable.
  • p preferably represents a number of 2 or more, more preferably represents a number of 3 or more, and a number of 18 or less. Is preferable, and it is more preferable to represent a number of 12 or less.
  • q preferably represents a number of 1 or more, more preferably a number of 2 or more, and a number of 10 or less. Is preferable, and it is more preferable to represent a number of 8 or less.
  • a skeleton represented by the above formula (X) having a group represented by the above formulas (A1), (A2), (A3), (A4), (A5), (A6) and (A7) is formed.
  • the compounds that can be made will be further described. Further, it is represented by the above formula (X) having a group different from the groups represented by the above formulas (A1), (A2), (A3), (A4), (A5), (A6) and (A7).
  • Compounds and the like capable of forming a skeleton will be further described.
  • the structure represented by the above formula (X) can be obtained, for example, by reacting a diamine compound with 3,3', 4,4'-biphenyltetracarboxylic dianhydride.
  • the diamine compound may be an aliphatic diamine compound, or may be a diamine compound different from the aliphatic diamine compound.
  • Examples of the aliphatic diamine compound include dimer diamine, tricyclodecanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornan, 3 (4), 8. (9) -Bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis (cyclohexylamine) , And 4,4'-methylenebis (2-methylcyclohexylamine) and the like. Only one type of aliphatic diamine compound may be used, or two or more types may be used in combination.
  • dimer diamine examples include Versamine 551 (trade name, manufactured by BASF Japan Ltd., 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552 (trade name). , Cognix Japan Co., Ltd., hydrogenated Versamine 551), and PRIAMINE 1075, PRIAMINE 1074 (trade name, all manufactured by Claude Japan Co., Ltd.) and the like.
  • Versamine 551 trade name, manufactured by BASF Japan Ltd., 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene
  • Versamine 552 trade name
  • Cognix Japan Co., Ltd. hydrogenated Versamine 551
  • PRIAMINE 1075, PRIAMINE 1074 trade name, all manufactured by Claude Japan Co., Ltd.
  • the dimer diamine is preferably a dimer diamine of "PRIAMINE 1075" manufactured by Croda Japan.
  • the dimer diamine is preferably a dimer diamine of "PRIAMINE 1074" manufactured by Croda Japan.
  • the aliphatic diamine compound is preferably a compound having 36 or less carbon atoms.
  • the aliphatic diamine compound is dimerdiamine, tricyclodecanediamine, bis (aminomethyl) norbornan, isophoronediamine or 4,4'-methylenebis (2-). Methylcyclohexylamine) is preferred. From the viewpoint of exerting the effects of the present invention even more effectively, the aliphatic diamine compound is more preferably dimerdiamine, tricyclodecanediamine, or bis (aminomethyl) norbornane.
  • the compound X has, for example, a group represented by the above formula (A5).
  • the compound X When the aliphatic diamine compound is tricyclodecanediamine, the compound X has, for example, a group represented by the above formula (A6). When the aliphatic diamine compound is a dimer diamine, the compound X has, for example, a group represented by the above formula (A7).
  • Examples of the diamine compound different from the above aliphatic diamine compounds include 1,1-bis (4-aminophenyl) cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, and 4,4'-methylenebis (2).
  • the diamine compound different from the above aliphatic diamine compound may be an aromatic diamine having a phenolic hydroxyl group. In this case, the coefficient of linear expansion can be further reduced.
  • the compound X may have a skeleton derived from a reaction product of a diamine compound and an acid dianhydride other than 3,3', 4,4'-biphenyltetracarboxylic dianhydride.
  • Examples of the acid dianhydride other than the above 3,3', 4,4'-biphenyltetracarboxylic dianhydride include tetracarboxylic dianhydride and the like.
  • Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, and 3,3', 4,4'-biphenylsulfone tetra.
  • the compound X preferably has a maleimide skeleton.
  • the number of maleimide skeletons in the above compound X is preferably 2 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
  • the number of the maleimide skeletons is at least the above lower limit and at least the above upper limit, the effect of the present invention can be more effectively exhibited.
  • the compound X preferably has a maleimide skeleton at both ends.
  • the compound X may or may not have a branched structure.
  • the compound X preferably has a structure represented by the following formula (Y).
  • R1 represents a tetravalent organic group
  • R2 represents an organic group
  • m represents a number of 1 or more.
  • m preferably represents a number of 2 or more, preferably represents a number of 20 or less, and more preferably represents a number of 10 or less.
  • R1 includes a skeleton having no biphenyl skeleton, and for example, an acid dianhydride other than the above-mentioned 3,3', 4,4'-biphenyltetracarboxylic dianhydride.
  • the skeleton from which it is derived can be mentioned.
  • R2 an organic group similar to the organic group of R in the above formula (X) can be mentioned.
  • R1 does not have a skeleton derived from phthalimide in the above formula (Y). From the viewpoint of exerting the effect of the present invention even more effectively, it is preferable that R1 does not have an aromatic skeleton in the above formula (Y).
  • R2 does not have a skeleton derived from phthalimide in the above formula (Y).
  • the above formula (X) out of a total of 100% of the number of repetitions (n) of the structure represented by the above formula (X) and the number of repetitions (m) of the structure represented by the above formula (Y).
  • the number of repetitions (n) of the structure represented by) is preferably 10% or more, more preferably 20% or more, preferably 90% or less, more preferably 75% or less, still more preferably 60% or less. In this case, the effect of the present invention can be exhibited even more effectively.
  • the compound X may have an even number of imide skeletons, may have an odd number of imide skeletons, and is a compound having an even number of imide skeletons and a compound having an odd number of imide skeletons. It may be a mixture.
  • the above compound X can be synthesized, for example, as follows.
  • the diamine compound, dimer diamine, and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are reacted to obtain the first reaction product.
  • the obtained first reactant is reacted with maleic anhydride.
  • compound X having a dimer diamine skeleton at the terminal can be synthesized, for example, as follows.
  • the diamine compound is reacted with 3,3', 4,4'-biphenyltetracarboxylic dianhydride to obtain a first reactant having an acid anhydride structure at both ends.
  • the obtained first compound is reacted with a dimer diamine to obtain a second reactant.
  • the obtained second reactant is reacted with maleic anhydride.
  • the weight average molecular weight of the compound X is preferably 1000 or more, more preferably 3100 or more, still more preferably 4500 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 25,000 or less, particularly preferably 18,000 or less. It is preferably 15,000 or less.
  • the coefficient of linear expansion can be further reduced.
  • the weight average molecular weight exceeds 25,000, the melt viscosity of the resin material becomes higher and the embedding property in the uneven surface may decrease as compared with the case where the weight average molecular weight is 25,000 or less.
  • the weight average molecular weight of the above compound X indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
  • the glass transition temperature of the compound X is preferably 70 ° C. or higher, more preferably 85 ° C. or higher. Is.
  • the glass transition temperature is set by heating in a nitrogen atmosphere from ⁇ 30 ° C. to 260 ° C. at a heating rate of 3 ° C./min using a differential scanning calorimetry device (for example, “Q2000” manufactured by TA Instruments). It can be obtained from the inflection point of the reverse heat flow.
  • a differential scanning calorimetry device for example, “Q2000” manufactured by TA Instruments.
  • the content of the compound X is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, preferably 10% by weight or more, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Is 80% by weight or less, more preferably 70% by weight or less, still more preferably 50% by weight or less.
  • the content of the compound X is at least the above lower limit, the dielectric loss tangent of the cured product can be further lowered and the desmear property can be further enhanced.
  • the content of the compound X is not more than the above upper limit, the surface roughness of the resin material after the desmear treatment can be lowered, and the embedding property in the unevenness of the substrate or the like can be improved.
  • the resin material preferably contains a thermosetting compound having no structure represented by the following formula (100).
  • the thermosetting compound is a thermosetting compound different from the compound X. Only one type of the thermosetting compound may be used, or two or more types may be used in combination.
  • R represents an organic group and n represents a number of 1 or more.
  • thermosetting compound examples include phenoxy compounds, oxetane compounds, maleimide compounds, epoxy compounds, cyanate compounds, vinyl compounds, polyarylate compounds, diallylphthalate compounds, episulfide compounds, (meth) acrylic compounds, amino compounds, and unsaturated polyester compounds. , Polyurethane compounds, silicone compounds and the like.
  • the thermosetting compound is preferably a maleimide compound, an epoxy compound, or a vinyl compound, more preferably contains an epoxy compound or a vinyl compound, and further preferably contains an epoxy compound.
  • the vinyl compound preferably contains a styrene compound or an acrylate compound, and preferably contains a styrene compound. In this case, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further improved.
  • the maleimide compound is a maleimide compound having no structure represented by the above formula (100).
  • the maleimide compound is a maleimide compound different from the compound X.
  • the maleimide compound may be a citraconimide compound. Only one type of the maleimide compound may be used, or two or more types may be used in combination.
  • the maleimide compound may be a bismaleimide compound.
  • maleimide compound examples include N-phenylmaleimide and N-alkylbismaleimide.
  • the maleimide compound may or may not have a skeleton derived from a diamine compound other than dimerdiamine or a triamine compound other than trimertriamine.
  • the maleimide compound preferably has an aromatic skeleton.
  • the nitrogen atom in the maleimide skeleton and the aromatic ring are bonded.
  • the content of the maleimide compound is preferably 0.5% by weight or more, more preferably 1% by weight, based on 100% by weight of the components excluding the solvent in the resin material. % Or more, preferably 15% by weight or less, more preferably 10% by weight or less.
  • the content of the maleimide compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 2.5% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less. It is more preferably 35% by weight or less, still more preferably 20% by weight or less.
  • the content of the maleimide compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.
  • the molecular weight of the maleimide compound is preferably 500 or more, more preferably 1000 or more, preferably less than 30,000, and more preferably less than 20,000.
  • the molecular weight of the maleimide compound means a molecular weight that can be calculated from the structural formula when the maleimide compound is not a polymer and when the structural formula of the maleimide compound can be specified.
  • the molecular weight of the maleimide compound indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) when the maleimide compound is a polymer.
  • Examples of commercially available maleimide compounds include “BMI4000” and “BMI5100” manufactured by Daiwa Kasei Kogyo Co., Ltd., “MIR-3000” manufactured by Nippon Kayaku Co., Ltd., and Designer Moleculars Inc. Examples thereof include “BMI-3000” and “BMI-689” manufactured by Japan.
  • Epoxy compound a conventionally known epoxy compound can be used.
  • the epoxy compound is an organic compound having at least one epoxy group. Only one type of the epoxy compound may be used, or two or more types may be used in combination.
  • Examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, biphenol type epoxy compound, and naphthalene type epoxy compound.
  • Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus as a skeleton.
  • the epoxy compound may be a glycidyl ether compound.
  • the glycidyl ether compound is a compound having at least one glycidyl ether group.
  • the epoxy compound may be an epoxy compound having a fluorine atom.
  • the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and has a naphthalene skeleton or a phenyl skeleton. It is preferable to contain an epoxy compound having an epoxy compound, and more preferably an epoxy compound having an aromatic skeleton.
  • the epoxy compound contains a liquid epoxy compound at 25 ° C. and a solid epoxy compound at 25 ° C. Is preferable.
  • the viscosity of the epoxy compound liquid at 25 ° C. at 25 ° C. is preferably 1000 mPa ⁇ s or less, and more preferably 500 mPa ⁇ s or less.
  • the viscosity of the epoxy compound can be measured using, for example, a dynamic viscoelasticity measuring device (“VAR-100” manufactured by Leologica Instruments) or the like.
  • VAR-100 dynamic viscoelasticity measuring device
  • the molecular weight of the epoxy compound is more preferably 1000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged product is laminated on the circuit board, the inorganic filler can be uniformly present.
  • the molecular weight of the epoxy compound means a molecular weight that can be calculated from the structural formula when the epoxy compound is not a polymer and the structural formula of the epoxy compound can be specified.
  • the epoxy compound is a polymer, it means the weight average molecular weight.
  • the content of the epoxy compound is preferably 4% by weight or more, more preferably 7% by weight or more, based on 100% by weight of the components excluding the solvent in the resin material. It is preferably 15% by weight or less, more preferably 12% by weight or less.
  • the content of the epoxy compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 15% by weight or more, more preferably 25% by weight or more, preferably 50% by weight or less, more preferably. Is 40% by weight or less.
  • the content of the epoxy compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.
  • the weight ratio of the content of the epoxy compound to the total content of the compound X and the curing agent described later is It is preferably 0.2 or more, more preferably 0.3 or more.
  • the weight ratio of the content of the epoxy compound to the total content of the compound X and the curing agent described later is It is preferably 1 or less, more preferably 0.8 or less.
  • the vinyl compound a conventionally known vinyl compound can be used.
  • the vinyl compound is an organic compound having at least one vinyl group. Only one kind of the vinyl compound may be used, or two or more kinds thereof may be used in combination.
  • Examples of the vinyl compound include styrene compounds, acrylate compounds, and divinyl compounds.
  • Examples of the divinyl compound include a divinylbenzyl ether compound.
  • the vinyl compound may be a divinyl compound having an aliphatic skeleton or a divinyl ether compound.
  • styrene compound examples include terminal styrene-modified phenylene ether compounds. Only one kind of the styrene compound may be used, or two or more kinds may be used in combination.
  • Examples of commercially available styrene compounds include "OPE-2St” manufactured by Mitsubishi Gas Chemical Company.
  • thermosetting compound preferably contains a radical curable compound.
  • the resin material preferably contains a radical curable compound.
  • the content of the vinyl compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more. Is 80% by weight or less, more preferably 70% by weight or less.
  • the content of the vinyl compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.
  • the resin material preferably contains an inorganic filler.
  • an inorganic filler By using the above-mentioned inorganic filler, the dielectric loss tangent of the cured product can be further lowered. Further, by using the above-mentioned inorganic filler, the dimensional change due to heat of the cured product is further reduced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds may be used in combination.
  • examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, diamond, aluminum nitride, and boron nitride.
  • the inorganic filler is preferably an inorganic filler having a thermal conductivity of 10 W / mK or more, such as alumina and boron nitride. In this case, heat dissipation can be improved.
  • the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica.
  • the silica may be hollow silica. Due to the use of silica, the coefficient of thermal expansion of the cured product is further reduced, and the dielectric loss tangent of the cured product is further reduced. Further, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased.
  • the shape of silica is preferably spherical.
  • the inorganic filler is spherical silica from the viewpoint of advancing the curing of the resin regardless of the curing environment, effectively increasing the glass transition temperature of the cured product, and effectively reducing the coefficient of linear thermal expansion of the cured product. Is preferable.
  • the inorganic filler is preferably alumina or boron nitride.
  • boron nitride since boron nitride has anisotropy, the coefficient of linear thermal expansion can be further reduced.
  • the average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, further preferably 500 nm or more, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, still more preferably 1 ⁇ m or less.
  • the average particle size of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness after etching can be reduced and the plating peel strength can be increased, and the insulating layer and the metal layer can be combined. Adhesion can be further improved.
  • the average particle size of the inorganic filler As the average particle size of the inorganic filler, a value of median diameter (d50) of 50% is adopted. The average particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device. When the inorganic filler is agglomerated particles, the average particle size of the inorganic filler means the primary particle diameter.
  • the inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased.
  • the aspect ratio of the inorganic filler is preferably 2 or less, more preferably 1.5 or less.
  • the inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and further preferably a surface-treated product with a silane coupling agent.
  • a surface-treated product with a coupling agent By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be obtained in the cured product. Can be granted.
  • Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like.
  • Examples of the silane coupling agent include methacrylsilane, acrylicsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.
  • the content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and particularly preferably 68% by weight in 100% by weight of the component excluding the solvent in the resin material. % Or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less.
  • the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered.
  • the content of the inorganic filler is not more than the above upper limit, the thermal dimensional stability can be improved and the warpage of the cured product can be effectively suppressed.
  • the content of the inorganic filler is at least the above lower limit and at least the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done. Further, the content of this inorganic filler makes it possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.
  • the resin material preferably contains a curing agent.
  • the curing agent is not particularly limited. A conventionally known curing agent can be used as the curing agent. Only one kind of the above-mentioned curing agent may be used, or two or more kinds may be used in combination.
  • the curing agent examples include a phenol compound (phenol curing agent), an active ester compound, a cyanate ester compound (cyanate ester curing agent), a benzoxazine compound having no imide bond (benzoxazine curing agent), and a carbodiimide compound (carbodiimide curing agent). ), Amine compound (amine curing agent), thiol compound (thiol curing agent), phosphine compound, dicyandiamide, acid anhydride and the like.
  • the curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.
  • the curing agent includes a phenol compound, an active ester compound, a cyanate ester compound, a benzoxazine compound having no imide bond, a carbodiimide compound, and an acid anhydride. It is preferable to contain at least one component in the substance. From the viewpoint of further enhancing the thermal dimensional stability and further lowering the dielectric adjacency, the curing agent is one of the phenol compound, the active ester compound, the cyanate ester compound, the benzoxazine compound having no imide bond, and the carbodiimide compound. It is more preferable to contain at least one component of the above, and it is further preferable to contain an active ester compound.
  • thermosetting compound contains an epoxy compound and the curing agent contains both a phenol compound and an active ester compound.
  • phenol compound examples include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.
  • phenol compounds include novolac-type phenol (“TD-2091” manufactured by DIC), biphenyl novolac-type phenol (“MEH-7851” manufactured by Meiwa Kasei Co., Ltd.), and aralkyl-type phenol compound (“MEH” manufactured by Meiwa Kasei Co., Ltd.). -7800 "), and phenols having an aminotriazine skeleton (“LA-1356” and "LA-3018-50P” manufactured by DIC) and the like can be mentioned.
  • the active ester compound is a compound containing at least one ester bond in the structure and having an aliphatic chain, an aliphatic ring or an aromatic ring bonded to both sides of the ester bond.
  • the active ester compound is obtained, for example, by a condensation reaction of a carboxylic acid compound or a thiocarboxylic acid compound with a hydroxy compound or a thiol compound.
  • Examples of the active ester compound include a compound represented by the following formula (1).
  • X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring or a group containing an aromatic ring
  • X2 represents a group containing an aromatic ring
  • Preferred examples of the group containing an aromatic ring include a benzene ring which may have a substituent and a naphthalene ring which may have a substituent.
  • the substituent include a hydrocarbon group.
  • the hydrocarbon group has preferably 12 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.
  • the combination of X1 and X2 includes a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a substituent. Examples thereof include a combination of a benzene ring and a naphthalene ring which may have a substituent. Further, in the above formula (1), examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.
  • the above active ester compound is not particularly limited. From the viewpoint of further enhancing thermal dimensional stability and flame retardancy, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable that the active ester compound has a naphthalene ring or a dicyclopentadiene skeleton in the main chain skeleton.
  • the resin material contains the epoxy compound and the active ester compound
  • Examples of commercially available products of the active ester compound include "HPC-8000-65T”, “EXB9416-70BK”, “EXB8100-65T”, “HPC-8150-62T” and “EXB-8" manufactured by DIC Corporation. ..
  • the active ester compound is preferably an ester compound having low molecular activity.
  • Examples of commercially available products of ester compounds having low molecular weight activity include the above-mentioned "EXB-8" manufactured by DIC Corporation.
  • Examples of the cyanate ester compound include a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and a prepolymer in which these are partially triquantized.
  • Examples of the novolak type cyanate ester resin include phenol novolac type cyanate ester resin and alkylphenol type cyanate ester resin.
  • Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethylbisphenol F type cyanate ester resin.
  • cyanate ester compound Commercially available products of the cyanate ester compound include a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan) and a prepolymer in which a bisphenol type cyanate ester resin is triquantized (Lonza Japan). Examples thereof include “BA-230S”, “BA-3000S”, “BTP-1000S” and “BTP-6020S”) manufactured by the same company.
  • the content of the cyanate ester compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more. It is preferably 85% by weight or less, more preferably 75% by weight or less.
  • the content of the cyanate ester compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.
  • benzoxazine compound having no imide bond examples include Pd-type benzoxazine and Fa-type benzoxazine.
  • benzoxazine compounds having no imide bond examples include “Pd type” manufactured by Shikoku Chemicals Corporation and “ODA-BOZ” manufactured by JFE Chemicals Corporation.
  • the content of the benzoxazine compound having no imide bond is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 5% by weight or more, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Is 10% by weight or more, preferably 70% by weight or less, and more preferably 60% by weight or less.
  • the content of the benzoxazine compound having no imide bond is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent of the cured product can be lowered and the thermal dimensional stability can be further improved.
  • the carbodiimide compound is a compound having a structural unit represented by the following formula (2).
  • the right end and the left end are binding sites for other groups. Only one kind of the carbodiimide compound may be used, or two or more kinds may be used in combination.
  • X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, a group in which a substituent is bonded to a cycloalkylene group, an arylene group, or a substituent bonded to an arylene group. It represents a group, and p represents an integer from 1 to 5. When a plurality of X's exist, the plurality of X's may be the same or different.
  • At least one X is an alkylene group, a group in which a substituent is attached to an alkylene group, a cycloalkylene group, or a group in which a substituent is attached to a cycloalkylene group.
  • carbodiimide compounds Commercially available products of the above carbodiimide compounds include “carbodilite V-02B”, “carbodilite V-03”, “carbodilite V-04K”, “carbodilite V-07”, “carbodilite V-09”, and “carbodilite” manufactured by Nisshinbo Chemical Co., Ltd. Examples thereof include “10M-SP” and “carbodilite 10M-SP (revised)", and "Stavaxol P", “Stavaxol P400” and "Hycazil 510" manufactured by Rheinchemy.
  • acid anhydride examples include tetrahydrophthalic anhydride, alkylstyrene-maleic anhydride copolymer and the like.
  • Examples of commercially available products of the acid anhydride include "Recasid TDA-100" manufactured by New Japan Chemical Co., Ltd.
  • the content of the curing agent with respect to 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less.
  • the content of the curing agent is at least the above lower limit and at least the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component can be further suppressed.
  • the total content of the compound X, the thermosetting compound, and the curing agent in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 40% by weight or more, more preferably 60. By weight or more, preferably 98% by weight or less, more preferably 95% by weight or less.
  • the curability is further improved and the thermal dimensional stability can be further enhanced.
  • the resin material contains a curing accelerator.
  • the curing rate becomes even faster.
  • the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result, the crosslinked density increases.
  • the curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one type of the curing accelerator may be used, or two or more types may be used in combination.
  • curing accelerator examples include anionic curing accelerators such as imidazole compounds, cationic curing accelerators such as amine compounds, and curing accelerators other than anionic and cationic curing accelerators such as phosphorus compounds and organic metal compounds. , And radical curing accelerators such as peroxides.
  • imidazole compound examples include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-.
  • 2-Methylimidazole 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6- [2' -Methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-ethyl-4'-methyl
  • amine compound examples include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4,4-dimethylaminopyridine and the like.
  • Examples of the phosphorus compound include triphenylphosphine compounds.
  • organometallic compound examples include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II) and trisacetylacetonate cobalt (III).
  • peroxide examples include dicumyl peroxide and perhexyl 25B.
  • the curing accelerator preferably contains the anionic curing accelerator, and more preferably contains the imidazole compound.
  • the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 20% by weight or more, based on 100% by weight of the curing accelerator. Is 50% by weight or more, more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.
  • the curing accelerator may contain the radical curing accelerator. preferable.
  • the content of the curing accelerator is not particularly limited.
  • the content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Hereinafter, it is more preferably 3% by weight or less.
  • the content of the curing accelerator is at least the above lower limit and at least the above upper limit, the resin material is efficiently cured. If the content of the curing accelerator is in a more preferable range, the storage stability of the resin material becomes even higher, and a better cured product can be obtained.
  • the resin material preferably contains a thermoplastic resin.
  • the thermoplastic resin include polyvinyl acetal resin, polyimide resin, phenoxy resin, and styrene butadiene resin. Only one type of the above-mentioned thermoplastic resin may be used, or two or more types may be used in combination.
  • the thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively improving the adhesion of metal wiring regardless of the curing environment.
  • the use of the phenoxy resin suppresses deterioration of the embedding property of the resin film in the holes or irregularities of the circuit board and non-uniformity of the inorganic filler. Further, by using the phenoxy resin, the melt viscosity can be adjusted, so that the dispersibility of the inorganic filler is improved, and the resin composition or the B-staged product is less likely to wet and spread in an unintended region during the curing process.
  • the phenoxy resin contained in the above resin material is not particularly limited.
  • As the phenoxy resin a conventionally known phenoxy resin can be used. Only one type of the phenoxy resin may be used, or two or more types may be used in combination.
  • phenoxy resins having skeletons such as bisphenol A type skeleton, bisphenol F type skeleton, bisphenol S type skeleton, biphenyl skeleton, novolak skeleton, naphthalene skeleton and imide skeleton.
  • Examples of commercially available products of the phenoxy resin include “YP50”, “YP55” and “YP70” manufactured by Nippon Steel & Sumikin Chemical Corporation, and “1256B40", “4250”, “4256H40” and “4275” manufactured by Mitsubishi Chemical Corporation. , “YX6954BH30” and “YX8100BH30” and the like.
  • the thermoplastic resin is preferably a polyimide resin (polyimide compound) from the viewpoint of improving handleability, plating peel strength at low roughness, and adhesion between the insulating layer and the metal layer.
  • the polyimide compound is preferably a polyimide compound obtained by a method of reacting a tetracarboxylic dianhydride with an aliphatic diamine compound.
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetra.
  • Examples of the aliphatic diamine include dimer diamine and the like.
  • Examples of the dimer diamine include Versamine 551 (trade name: BASF Japan Ltd., 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552 (trade name, trade name, Examples thereof include Cognix Japan Co., Ltd., a hydrogenated product of Versamine 551), PRIAMINE1075, PRIAMINE1074 (trade name, all manufactured by Crowder Japan Co., Ltd.) and the like.
  • the polyimide compound may have an acid anhydride structure, a maleimide structure, or a citraconimide structure at the terminal.
  • the polyimide compound and the epoxy compound can be reacted.
  • the thermal dimensional stability of the cured product can be improved.
  • the weight average molecular weights of the thermoplastic resin, the polyimide resin and the phenoxy resin are preferably 10,000 or more, more preferably 15,000 or more, preferably 100,000 or less. It is preferably 50,000 or less.
  • the weight average molecular weights of the thermoplastic resin, the polyimide resin, and the phenoxy resin indicate the polystyrene-equivalent weight average molecular weights measured by gel permeation chromatography (GPC).
  • the contents of the thermoplastic resin, the polyimide resin, and the phenoxy resin are not particularly limited.
  • the content of the thermoplastic resin in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin). ) Is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less.
  • the content of the thermoplastic resin is at least the above lower limit and at least the above upper limit, the embedding property of the resin material in the holes or irregularities of the circuit board is improved.
  • the content of the thermoplastic resin is at least the above lower limit, the formation of the resin film becomes easier and a better insulating layer can be obtained.
  • the content of the thermoplastic resin is not more than the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower.
  • the content of the thermoplastic resin is not more than the above upper limit, the surface roughness of the surface of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.
  • the resin material does not contain or contains a solvent.
  • the viscosity of the resin material can be controlled in a suitable range, and the coatability of the resin material can be improved.
  • the solvent may be used to obtain a slurry containing the inorganic filler. Only one type of the solvent may be used, or two or more types may be used in combination.
  • Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, and methyl ethyl ketone.
  • Examples thereof include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone and naphtha as a mixture.
  • the boiling point of the solvent is preferably 200 ° C. or lower, more preferably 180 ° C. or lower.
  • the content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coatability of the resin composition and the like.
  • the content of the solvent in 100% by weight of the B stage film is preferably 1% by weight or more, more preferably 2% by weight or more, and preferably 10% by weight or less. , More preferably 5% by weight or less.
  • the above resin materials include organic fillers, leveling agents, flame retardants, coupling agents, colorants, antioxidants, and UV deterioration prevention. It may contain an agent, a defoaming agent, a thickener, a rocking denaturing agent and the like.
  • the organic filler examples include particulate matter made of benzoxazine resin, benzoxazole resin, fluororesin, acrylic resin, styrene resin and the like.
  • the fluororesin examples include polytetrafluoroethylene (PTFE) and the like.
  • PTFE polytetrafluoroethylene
  • the average particle size of the organic filler is preferably 1 ⁇ m or less. When the average particle size of the organic filler is not more than the above upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be improved. It can be further enhanced.
  • the average particle size of the organic filler may be 50 nm or more.
  • the average particle size of the organic filler As the average particle size of the organic filler, a value of median diameter (d50) of 50% is adopted.
  • the average particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device.
  • Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like.
  • Examples of the silane coupling agent include vinylsilane, aminosilane, imidazolesilane, and epoxysilane.
  • a resin film (B-staged product / B-stage film) can be obtained by molding the above-mentioned resin composition into a film.
  • the resin material is preferably a resin film.
  • the resin film is preferably a B stage film.
  • Examples of the method for obtaining a resin film by molding the resin composition into a film form include the following methods.
  • An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film by a T-die, a circular die, or the like.
  • a casting molding method in which a resin composition containing a solvent is cast and molded into a film.
  • An extrusion molding method or a casting molding method is preferable because it can be made thinner.
  • the film includes a sheet.
  • a resin film as a B-stage film can be obtained by molding the resin composition into a film and heating and drying it at 50 ° C. to 150 ° C. for 1 minute to 10 minutes to the extent that curing by heat does not proceed too much. it can.
  • the film-like resin composition that can be obtained by the drying step as described above is referred to as a B stage film.
  • the B stage film is in a semi-cured state.
  • the semi-cured product is not completely cured and can be further cured.
  • the resin film does not have to be a prepreg.
  • the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when the resin film is laminated or pre-cured, unevenness due to the glass cloth does not occur on the surface.
  • the resin film can be used in the form of a laminated film including a metal foil or a base film and a resin film laminated on the surface of the metal foil or the base material.
  • the metal foil is preferably a copper foil.
  • Examples of the base film of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, and polyimide resin films.
  • the surface of the base film may be mold-released, if necessary.
  • the thickness of the resin film is preferably 5 ⁇ m or more, preferably 200 ⁇ m or less.
  • the thickness of the insulating layer formed by the resin film is preferably equal to or larger than the thickness of the conductor layer (metal layer) forming the circuit.
  • the thickness of the insulating layer is preferably 5 ⁇ m or more, and preferably 200 ⁇ m or less.
  • the resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.
  • the above resin material is preferably used as an insulating material.
  • the resin material is preferably used for forming an insulating layer in a printed wiring board.
  • the printed wiring board can be obtained, for example, by heat-press molding the resin material.
  • a member to be laminated having a metal layer on one side or both sides can be laminated on the resin film.
  • a laminated structure comprising a member to be laminated having a metal layer on its surface and a resin film laminated on the surface of the metal layer, and the resin film being the resin material described above can be preferably obtained.
  • the method of laminating the resin film and the member to be laminated having the metal layer on the surface is not particularly limited, and a known method can be used. For example, using a device such as a parallel flat plate press or a roll laminator, the resin film can be laminated on a member to be laminated having a metal layer on the surface while pressurizing with or without heating.
  • the material of the metal layer is preferably copper.
  • the member to be laminated having the metal layer on the surface may be a metal foil such as a copper foil.
  • the above resin material is suitably used for obtaining a copper-clad laminate.
  • An example of the copper-clad laminate is a copper-clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil.
  • the thickness of the copper foil of the copper-clad laminate is not particularly limited.
  • the thickness of the copper foil is preferably in the range of 1 ⁇ m to 50 ⁇ m.
  • the copper foil has fine irregularities on the surface.
  • the method of forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a method for forming the unevenness by a treatment using a known chemical solution.
  • the above resin material is preferably used to obtain a multilayer substrate.
  • the multilayer board is a multilayer board provided with a circuit board and an insulating layer laminated on the circuit board.
  • the insulating layer of this multilayer substrate is formed of the above resin material. Further, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film by using the laminated film.
  • the insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. It is preferable that a part of the insulating layer is embedded between the circuits.
  • the surface of the insulating layer opposite to the surface on which the circuit board is laminated is roughened.
  • the roughening treatment method can be a conventionally known roughening treatment method, and is not particularly limited.
  • the surface of the insulating layer may be swelled before the roughening treatment.
  • the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.
  • the circuit board, the insulating layer laminated on the surface of the circuit board, and the insulating layer are laminated on the surface opposite to the surface on which the circuit board is laminated.
  • Examples thereof include a multilayer substrate provided with a copper foil.
  • the insulating layer is formed by curing the resin film using a copper-clad laminate having a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil is etched and preferably a copper circuit.
  • the multilayer board there is a multilayer board provided with a circuit board and a plurality of insulating layers laminated on the surface of the circuit board. At least one of the plurality of insulating layers arranged on the circuit board is formed by using the resin material. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed by using the resin film.
  • multilayer printed wiring boards are required to have low dielectric loss tangent and high insulation reliability due to the insulating layer.
  • the insulation reliability can be effectively improved by lowering the dielectric loss tangent and improving the adhesion and etching performance between the insulating layer and the metal layer. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.
  • the multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers. At least one of the insulating layers is a cured product of the resin material.
  • FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to an embodiment of the present invention.
  • a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12.
  • the insulating layers 13 to 16 are cured products layers.
  • a metal layer 17 is formed in a part of the upper surface 12a of the circuit board 12.
  • metal layers 17 are formed in a part of the upper surface of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. ing.
  • the metal layer 17 is a circuit.
  • a metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between the layers of the laminated insulating layers 13 to 16, respectively.
  • the lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).
  • the insulating layers 13 to 16 are formed of a cured product of the above resin material.
  • the surfaces of the insulating layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the insulating layers 13 to 16.
  • the metal layer 17 reaches the inside of the fine pores.
  • the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the portion where the metal layer 17 is not formed can be reduced.
  • good insulation reliability is imparted between the upper metal layer and the lower metal layer which are not connected by via hole connection and through hole connection (not shown).
  • the resin material is preferably used to obtain a cured product to be roughened or desmeared.
  • the cured product also includes a pre-cured product that can be further cured.
  • the cured product is preferably roughened in order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material.
  • the cured product Prior to the roughening treatment, the cured product is preferably swelled. It is preferable that the cured product is swelled and further cured after the roughening treatment after the pre-curing and before the roughening treatment. However, the cured product does not necessarily have to be swelled.
  • the method for the swelling treatment for example, a method of treating the cured product with an aqueous solution of a compound containing ethylene glycol or the like as a main component or an organic solvent dispersion solution is used.
  • the swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like.
  • the swelling liquid preferably contains sodium hydroxide.
  • the swelling treatment is carried out by treating the cured product at a treatment temperature of 30 ° C. to 85 ° C. for 1 minute to 30 minutes using a 40 wt% ethylene glycol aqueous solution or the like.
  • the temperature of the swelling treatment is preferably in the range of 50 ° C. to 85 ° C. If the temperature of the swelling treatment is too low, the swelling treatment takes a long time, and the adhesive strength between the cured product and the metal layer tends to be low.
  • a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added.
  • the roughening solution used for the roughening treatment generally contains an alkali as a pH adjuster or the like.
  • the roughening solution preferably contains sodium hydroxide.
  • Examples of the manganese compound include potassium permanganate and sodium permanganate.
  • Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate.
  • Examples of the persulfate compound include sodium persulfate, potassium persulfate, ammonium persulfate and the like.
  • the arithmetic mean roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and further preferably less than 150 nm.
  • the adhesive strength between the cured product and the metal layer is increased, and the surface of the insulating layer forms finer wiring. Further, the conductor loss can be suppressed, and the signal loss can be suppressed low.
  • the arithmetic mean roughness Ra is measured according to JIS B0601: 1994.
  • Through holes may be formed in the cured product obtained by pre-curing the resin material.
  • Vias, through holes, and the like are formed as through holes in the multilayer substrate and the like.
  • vias can be formed by irradiation with a laser such as a CO 2 laser.
  • the diameter of the via is not particularly limited, but is about 60 ⁇ m to 80 ⁇ m. Due to the formation of the through holes, smear, which is a residue of the resin derived from the resin component contained in the cured product, is often formed at the bottom of the via.
  • the surface of the cured product is preferably desmear-treated.
  • the desmear treatment may also serve as the roughening treatment.
  • a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used in the same manner as in the roughening treatment.
  • These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added.
  • the desmear treatment liquid used for the desmear treatment generally contains an alkali.
  • the desmear treatment solution preferably contains sodium hydroxide.
  • the surface roughness of the surface of the desmear-treated cured product is sufficiently reduced.
  • Compound X-2 According to the following Synthesis Example 2, compound X-2 (molecular weight 4500) represented by the following formula (X-2) was synthesized. In the obtained compound X-2, the average ratio of the first skeleton derived from tricyclodecanediamine was 72 mol%, and the second skeleton derived from diamine diamine was in 100 mol% of the total structural units of the skeleton derived from the diamine compound. The average proportion of skeletons in was 28 mol%.
  • the following formula (X-2) is an example of compound X-2 obtained in Synthesis Example 2, and compound X-2 is obtained as a mixture of compounds having different amine positions.
  • NMP N-methyl-2-pyrrolidone
  • Compound X-3 According to the following Synthesis Example 3, compound X-3 (molecular weight 4200) represented by the following formula (X-3) was synthesized. In the obtained compound X-3, the average ratio of the first skeleton derived from tricyclodecanediamine was 75 mol% and the second skeleton derived from diamine diamine was derived from 100 mol% of the total structural units of the skeleton derived from the diamine compound. The average proportion of skeletons was 25 mol%.
  • the following formula (X-3) is an example of the compound X-3 obtained in Synthesis Example 3, and the compound X-3 is obtained as a mixture of compounds having different amine positions.
  • Compound Y-1 (molecular weight 3300) was synthesized according to Synthesis Example 4 below.
  • Compound Y-2 (molecular weight 5100) was synthesized according to Synthesis Example 5 below.
  • NMP N-methyl-2-pyrrolidone
  • GPC Gel Permeation Chromatography Measurement: A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used, and measurement was carried out using tetrahydrofuran (THF) as a developing medium at a column temperature of 40 ° C. and a flow velocity of 1.0 ml / min. "SPD-10A” was used as a detector, and two columns of "KF-804L” (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series.
  • THF tetrahydrofuran
  • the average ratio of each skeleton of the compounds X-2 and X-3 synthesized in Synthesis Examples 2 and 3 is 1 H-NMR measurement, and the hydrogen atom bonded to the carbon atom bonded to the nitrogen atom constituting each diamine skeleton. It was calculated from the area ratio of the signal of.
  • Silica-containing slurry (silica 75% by weight: "SC4050-HOA” manufactured by Admatex, average particle size 1.0 ⁇ m, aminosilane treatment, cyclohexanone 25% by weight)
  • polyimide resin A polyimide compound-containing solution (nonvolatile content 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to the following Synthesis Example 6.
  • PRIAMINE 1075 dimer diamine
  • 1,3-bisaminomethylcyclohexane manufactured by Mitsubishi Gas Chemical Company
  • the molecular weight of the polyimide compound synthesized in Synthesis Example 6 was determined as follows.
  • GPC Gel Permeation Chromatography Measurement: A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used, and measurement was carried out using tetrahydrofuran (THF) as a developing medium at a column temperature of 40 ° C. and a flow velocity of 1.0 ml / min. "SPD-10A” was used as a detector, and two columns of "KF-804L” (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series.
  • THF tetrahydrofuran
  • Examples 1 to 9 and Comparative Examples 1 to 5 The components shown in Tables 1 to 3 below were blended in the blending amounts (unit: parts by weight of solid content) shown in Tables 1 to 3 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.
  • Preparation of resin film After applying the obtained resin material on the release-treated surface of the release-treated PET film (Toray Industries, Inc. "XG284", thickness 25 ⁇ m) using an applicator, 2 minutes in a gear oven at 100 ° C. It was dried for 30 seconds to volatilize the solvent. In this way, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 ⁇ m is laminated on the PET film was obtained.
  • XG284 thickness 25 ⁇ m
  • Dielectric Dissipation Factor The obtained resin film was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was cut into a size of 2 mm in width and 80 mm in length, and 10 sheets were superposed, and "Cavity Resonance Permittivity Measuring Device CP521" manufactured by Kanto Denshi Applied Development Co., Ltd. and "Keysight Technology Co., Ltd.” Using a network analyzer N5224A PNA, the dielectric loss tangent was measured by the cavity resonance method at room temperature (23 ° C.) and at a frequency of 5.8 GHz.
  • Dissipation factor is less than 2.9 ⁇ 10 -3 ⁇ : Dissipation factor is 2.9 ⁇ 10 -3 or more
  • Via (through hole) formation Using a CO 2 laser (manufactured by Hitachi Via Mechanics) on the semi-cured resin film of the obtained laminate A, a via (penetration) having a diameter of 60 ⁇ m at the upper end and a diameter of 40 ⁇ m at the lower end (bottom). A hole) was formed. In this way, a laminated body B in which the semi-cured product of the resin film was laminated on the CCL substrate and vias (through holes) were formed in the semi-cured product of the resin film was obtained.
  • a CO 2 laser manufactured by Hitachi Via Mechanics
  • the bottom of the via of the evaluation sample 1 was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via was measured.
  • SEM scanning electron microscope
  • the laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then the pressure was pressed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Then, the resin film was semi-cured by heating at 180 ° C. for 30 minutes. In this way, a laminated body in which a semi-cured resin film was laminated on the CCL substrate was obtained.
  • ⁇ The average value of the arithmetic average roughness Ra is less than 50 nm ⁇ : The average value of the arithmetic average roughness Ra is 50 nm or more and less than 80 nm ⁇ : The average value of the arithmetic average roughness Ra is 80 nm or more
  • the laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, then laminating at 100 ° C. and pressure 0.7 MPa for 30 seconds, and further pressing at a press pressure of 0.8 MPa and a press temperature of 100 ° C. for 60 seconds. Then, the resin film in the laminated structure was heated at 100 ° C. for 30 minutes with the PET film attached, and then further heated at 180 ° C. for 30 minutes to semi-cure the resin film. Then, the PET film was peeled off to obtain a laminated body in which a semi-cured product of the resin film was laminated on the CCL substrate.
  • Electroless plating The surface of the obtained roughened cured product was treated with an alkaline cleaner at 60 ° C. (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and degreased and washed. After washing, the cured product was treated with a predip solution at 25 ° C. (“Predip Neogant B” manufactured by Atotech Japan) for 2 minutes. Then, the cured product was treated with an activator solution at 40 ° C. (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and a palladium catalyst was attached. Next, the cured product was treated with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.
  • an alkaline cleaner at 60 ° C. (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and degreased and washed. After washing
  • the cured product was placed in a chemical copper solution (Atotech Japan's "Basic Print Gantt MSK-DK”, “Copper Print Gantt MSK”, “Stabilizer Print Gantt MSK”, and “Reducer Cu”) for electroless plating.
  • a chemical copper solution Atotech Japan's "Basic Print Gantt MSK-DK”, “Copper Print Gantt MSK”, “Stabilizer Print Gantt MSK”, and "Reducer Cu
  • annealing treatment was performed at a temperature of 120 ° C. for 30 minutes in order to remove residual hydrogen gas. All the steps up to the electroless plating step were carried out with a beaker scale containing 2 L of the treatment liquid and shaking the cured product.
  • Electroplating Next, electroplating was performed on the cured product subjected to electroless plating until the plating thickness became 25 ⁇ m.
  • Copper sulfate solution for electrolytic copper plating (“Copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, Ltd., “Sulfate” manufactured by Wako Pure Chemical Industries, Ltd., "Basic leveler capallaside HL” manufactured by Atotech Japan, “Basic leveler capallaside HL” manufactured by Atotech Japan.
  • Capalacid GS electrolytic plating was carried out by passing a current of 0.6 A / cm 2 until the plating thickness became about 25 ⁇ m.
  • the cured product was heated at 200 ° C. for 60 minutes to further cure the cured product. In this way, a cured product in which the copper plating layer was laminated on the upper surface was obtained.
  • plating peel strength A total of 6 strip-shaped cuts having a width of 10 mm were made at 5 mm intervals on the surface of the cured copper plating layer on which the obtained copper plating layer was laminated on the upper surface.
  • the plating layer was peeled off by 20 mm and the peeling strength (plating peel strength) was measured.
  • the peeling strength (plating peel strength) was measured at each of the six notches, and the average value of the plating peel strength was obtained.
  • the plating peel strength was judged according to the following criteria.
  • Multi-layer printed wiring board 12 ... Circuit board 12a ... Top surface 13-16 ... Insulation layer 17 ... Metal layer

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne un matériau de résine. Selon l'invention, 1) le facteur de dissipation diélectrique d'un article durci constitué dudit matériau peut être abaissé, 2) la stabilité dimensionnelle thermique de l'article durci peut être augmentée, 3) la coulée de résine peut être efficacement éliminée par déglaçage, 4) la variation de rugosité de surface après gravure peut être supprimée, et 5) la résistance au pelage du placage peut être augmentée. Le matériau de résine selon la présente invention comprend un composé ayant une structure représentée par la formule (X), et un accélérateur de durcissement. Dans la formule (X), R représente un groupe organique, et n ≥ 1.
PCT/JP2020/029443 2019-08-01 2020-07-31 Matériau de résine et carte de circuit imprimé multicouche WO2021020563A1 (fr)

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WO2021182207A1 (fr) * 2020-03-13 2021-09-16 積水化学工業株式会社 Matériau de résine et carte de circuit imprimé multicouche
WO2022210433A1 (fr) * 2021-03-30 2022-10-06 日本化薬株式会社 Mélange de résine de maléimide, composition de résine durcissable, préimprégné et produit durci de celui-ci
WO2022210442A1 (fr) * 2021-03-30 2022-10-06 日本化薬株式会社 Composition de résine durcissable et objet durci obtenu à partir de celle-ci

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WO2022210433A1 (fr) * 2021-03-30 2022-10-06 日本化薬株式会社 Mélange de résine de maléimide, composition de résine durcissable, préimprégné et produit durci de celui-ci
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