WO2018097010A1 - Composition de résine, film thermodurcissable l'utilisant, produit de résine durcie, stratifié, carte de circuit imprimé et dispositif semiconducteur - Google Patents

Composition de résine, film thermodurcissable l'utilisant, produit de résine durcie, stratifié, carte de circuit imprimé et dispositif semiconducteur Download PDF

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Publication number
WO2018097010A1
WO2018097010A1 PCT/JP2017/041129 JP2017041129W WO2018097010A1 WO 2018097010 A1 WO2018097010 A1 WO 2018097010A1 JP 2017041129 W JP2017041129 W JP 2017041129W WO 2018097010 A1 WO2018097010 A1 WO 2018097010A1
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Prior art keywords
resin
resin composition
carbon atoms
component
thermosetting film
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PCT/JP2017/041129
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English (en)
Japanese (ja)
Inventor
佐藤　淳也
津与志 黒川
吉田　真樹
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ナミックス株式会社
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Priority to JP2018552527A priority Critical patent/JP6917636B2/ja
Priority to KR1020197013775A priority patent/KR102399159B1/ko
Priority to CN201780068677.0A priority patent/CN109923176B/zh
Publication of WO2018097010A1 publication Critical patent/WO2018097010A1/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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • B32B15/092—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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present disclosure relates to a resin composition, and a thermosetting film, a resin cured product, a laminated board, a printed wiring board, and a semiconductor device using the resin composition.
  • Dielectric properties are also used for interlayer adhesives used in multilayer printed wiring boards or adhesive films used as surface protective films (ie, coverlay films) of printed wiring boards.
  • it is required to show a low dielectric loss tangent (tan ⁇ ).
  • the dielectric constant in the frequency range of 1 to 10 GHz is required to be 3.5 or less
  • the dielectric loss tangent (tan ⁇ ) in the frequency range of 1 to 10 GHz is required to be 0.010 or less.
  • “ ⁇ ” in a numerical range means that numerical values described before and after the numerical value are included in the region. That is, the numerical range “X to Y” means X or more and Y or less.
  • an object of the present disclosure is to provide the following resin composition, a thermosetting film using the same, a cured resin, a laminated board, a printed wiring board, and a semiconductor device.
  • This thermosetting film has an excellent adhesive strength after curing to a metal foil contained in the wiring of the printed wiring board and a substrate material such as polyimide.
  • the thermosetting film exhibits dielectric properties in a high frequency region, specifically, a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency region of 1 to 100 GHz.
  • Said resin composition can be used for preparation of this thermosetting film.
  • one aspect (first aspect) of the present disclosure includes (A) epoxy resin, (B) a resin having a dielectric loss tangent (tan ⁇ ) of less than 0.005 in the frequency range of 1 to 100 GHz; and, (C) an imidazole compound in which a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring; The resin composition containing this is provided.
  • the (C) imidazole compound contained in the resin composition of the first aspect is preferably a compound represented by the following formula (I).
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • M is 0 or 1.
  • R 4 Is an alkylene group having 1 to 3 carbon atoms or —CH 2 CH 2 COO—, and R 5 is an alkyl group having 5 to 10 carbon atoms.
  • the resin (B) contained in the resin composition of the first aspect is preferably at least selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin.
  • modified PPE modified polyphenylene ether
  • styrene-based thermoplastic elastomer a polyimide resin.
  • the second aspect of the present disclosure provides a thermosetting film formed from the resin composition.
  • a third aspect of the present disclosure provides a cured resin product that is the cured resin composition or the thermosetting film.
  • the 4th aspect in this indication provides the laminated board containing the said resin hardened
  • the fifth aspect of the present disclosure provides a printed wiring board including the above resin cured product.
  • a sixth aspect of the present disclosure provides a semiconductor device including the resin cured product.
  • thermosetting film formed from the resin composition of the first aspect described above has excellent adhesion to a metal foil contained in the wiring of the printed wiring board and a substrate material such as polyimide after curing. It has strength and exhibits dielectric characteristics in a high frequency region, specifically, a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency region of 1 to 100 GHz.
  • the resin composition of this embodiment includes (A) an epoxy resin, (B) a resin having a dielectric loss tangent (tan ⁇ ) of less than 0.005 in the frequency range of 1 to 100 GHz, and (C) the first position of the heterocyclic ring.
  • an imidazole compound having a side chain containing an alkyl group having 5 or more carbon atoms is included.
  • Epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, siloxane type epoxy resin, biphenyl type epoxy resin. Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, epoxy resin having naphthalene skeleton, and epoxy resin having anthracene skeleton.
  • the compounds exemplified here may be used alone, or two or more compounds may be mixed and used.
  • the epoxy resin of component (A) preferably contains any of a biphenyl type epoxy resin, an epoxy resin having a naphthalene skeleton, and an epoxy resin having an anthracene skeleton.
  • a biphenyl type epoxy resin examples include NC-3000H manufactured by Nippon Kayaku Co., Ltd.
  • examples of commercially available epoxy resins having a naphthalene skeleton include HP4032D manufactured by DIC Corporation, and a commercially available anthracene skeleton.
  • As an example of the epoxy resin JERIX8800 manufactured by Mitsubishi Chemical Corporation can be given.
  • the epoxy resin of component (A) is preferably a naphthalene type epoxy resin.
  • the content of the epoxy resin as the component (A) is preferably 2 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 100 parts by mass in total of the components (A) and (B). 2 to 10 parts by mass.
  • the adhesiveness of the thermosetting film formed from the resin composition of this embodiment will deteriorate.
  • the amount of the component (A) is too large, the amount of the component (B) is relatively decreased, so that the dielectric properties in the high frequency region of the thermosetting film are deteriorated.
  • Component resin has a dielectric loss tangent (tan ⁇ ) of less than 0.005 in the frequency range of 1 to 100 GHz. This is because the thermosetting film formed from the resin composition of the present disclosure has excellent dielectric properties in a high frequency region, that is, a low dielectric constant ( ⁇ ) in a frequency region of 1 GHz or more and a low dielectric loss tangent. Contributes to (tan ⁇ ).
  • the resin of component (B) is preferably at least one resin selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene thermoplastic elastomer, and a polyimide resin. Only one of these resins may be used, or two or more resins may be used in combination.
  • modified PPE modified polyphenylene ether
  • a compound represented by the following general formula (1) is preferably used as the component (B), when a modified PPE resin is used.
  • — (O—X—O) — is represented by the following general formula (2) or (3).
  • R 1 , R 2 , R 3 , R 7 , and R 8 are alkyl groups or phenyl groups having 6 or less carbon atoms, and may be the same or different from each other.
  • R 4 , R 5 and R 6 are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other.
  • R 9, R 10, R 11, R 12, R 13, R 14, R 15 and R 16 is a hydrogen atom, an alkyl group or a phenyl group, the 6 or less carbon atoms, They may be the same or different from each other.
  • -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
  • — (YO) — is represented by the general formula (4).
  • one type of structure or two or more types of structures represented by the formula (4) are randomly arranged.
  • R 17 and R 18 are an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other.
  • R 19 and R 20 are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other.
  • a and b represent integers of 0 to 100. However, at least one of a and b is not 0.
  • Examples of -A- in formula (3) include methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1- And divalent organic groups such as methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.
  • this divalent organic group is not limited to these groups.
  • R 1 , R 2 , R 3 , R 7 , R 8 , R 17 , and R 18 are preferably an alkyl group having 3 or less carbon atoms
  • R 4 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 19 , and R 20 are a hydrogen atom or an alkyl group having 3 or less carbon atoms is there.
  • — (O—X—O) — represented by the general formula (2) or the general formula (3) is the general formula (5), the general formula (6), or the general formula (7).
  • — (YO) — represented by the general formula (4) is the formula (8) or the formula (9).
  • the method for producing the compound represented by the formula (1) is not particularly limited.
  • it can be produced by vinylbenzyl etherifying a terminal phenolic hydroxyl group of a bifunctional phenylene ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound.
  • the number average molecular weight of the compound represented by the formula (1) is preferably in the range of 500 to 3,000, more preferably in the range of 1000 to 2500 in terms of polystyrene by the GPC method.
  • the number average molecular weight is 500 or more, there is little stickiness when the resin composition of this embodiment is formed into a coating film.
  • a number average molecular weight is 3000 or less, the fall of the solubility to a solvent can be suppressed.
  • the styrene-based thermoplastic elastomer as the component (B) refers to a thermoplastic elastomer containing styrene, a homologue thereof, or an analogue thereof.
  • the styrenic thermoplastic elastomer as the component (B) include polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS), styrene- Examples include butadiene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and polybutadiene (PB).
  • SEEPS polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene
  • SEBS polystyrene-poly (ethylene / butylene) block-pol
  • One of the elastomers exemplified here may be used alone, or two or more elastomers may be mixed and used. From the viewpoint of improving the dielectric properties with respect to the metal foil contained in the wiring of the printed wiring board and the substrate material such as polyimide, SEEPS is preferable.
  • a solvent-soluble polyimide resin is preferably used.
  • solvent soluble means that 20% by weight or more is dissolved in at least one solvent selected from the solvents shown below at 23 ° C.
  • solvents include hydrocarbon solvents such as toluene, xylene, ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ether solvents 1,4-dioxane, tetrahydrofuran, diglyme, glycol ether solvents.
  • the solvent-soluble polyimide of the present embodiment can be obtained by reacting a diamine and a tetracarboxylic acid component at a temperature of 130 ° C. or higher to cause an imidization reaction.
  • the solvent-soluble polyimide is a polyimide resin having excellent flexibility, toughness, and heat resistance.
  • the polyimide resin is obtained by reacting a tetracarboxylic acid component with dimer diamine. In this reaction that produces a solvent-soluble polyimide, a portion of dimer diamine may be replaced by silicone diamine.
  • tetracarboxylic acid component examples include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone.
  • Tetracarboxylic dianhydride 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1, 2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxy) Enoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,
  • dimeramine examples include Versamine 551 (trade name, manufactured by BASF Japan Ltd .; 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)) cyclohexene) and Versamine 552 (trade name, manufactured by Cognics Japan, Inc .; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (both are trade names, manufactured by Croda Japan Co., Ltd.).
  • the solvent-soluble polyimide resin has a polyimide molecular structure generated by a reaction between a tetracarboxylic acid component and dimer diamine. An acid anhydride group or an amino group is present at the end of the molecular structure.
  • Dimer acid which is a raw material of dimeramine, can be obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms (a mixture of oleic acid, linoleic acid, linolenic acid, and the like). By the dimerization reaction, a mixture containing a reaction product having a linear chain, an alicyclic ring, an alicyclic ring having a double bond, or an aromatic ring in an amount corresponding to the reaction probability is obtained.
  • the solvent-soluble polyimide resin obtained by polymerization of tetracarboxylic acid and dimer diamine has a complicated molecular structure that is generated as a result of irregular binding of each molecule of dimer acid contained in the reaction mixture. This complex molecular structure cannot be clearly identified.
  • examples of molecular structures that can be inferred include molecular structures represented by the following chemical structural formulas.
  • the solvent-soluble polyimide resin used in this embodiment is considered to be a mixture of polyimide resins having these molecular structures. (These structural formulas are merely examples.
  • n is an integer.
  • R 10 , R 20 , R 30 , and R 40 are organic groups.
  • R 10 and R 20 are — (CH 2 ) n1 — (CH ⁇ CH) n2 — (CH 2 ) n3 —CH 3 and may be the same or different from each other.
  • R 30 and R 40 are — (CH 2 ) n1 — (CH ⁇ CH) n2 — (CH 2 ) n3 —, and may be the same or different from each other.
  • n1 and n3 are integers from 0 to 18.
  • n2 is an integer of 0, 1, or 2.
  • the total number of carbon atoms in the dimer diamine component is 36.
  • the resin content of the component (B) is preferably 70 to 98 parts by weight, more preferably 80 to 98 parts by weight, and still more preferably 90 to 98 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). 98 parts by mass.
  • resin content of the component (B) is preferably 70 to 98 parts by weight, more preferably 80 to 98 parts by weight, and still more preferably 90 to 98 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). 98 parts by mass.
  • the action of the (C) component imidazole compound varies depending on the resin used as the (B) component.
  • the resin used as the component (B) is a resin that causes a curing reaction with the epoxy resin of the component (A), such as a polyimide resin
  • the imidazole compound of the component (C) acts as a curing catalyst.
  • the resin used as component (B) is a resin that does not react with the epoxy resin of component (A), such as a modified PPE resin or a styrene thermoplastic elastomer
  • the imidazole compound of component (C) is ( A) It acts as a curing catalyst for the epoxy resin itself.
  • Imidazole compounds are conventionally used as curing agents or curing catalysts for epoxy resins.
  • an imidazole compound having a specific structure in which a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring as the component (C).
  • the thermosetting film formed from the resin composition has excellent adhesive strength with respect to the substrate material such as metal foil and polyimide contained in the wiring of the printed wiring board, and has a high frequency range.
  • the dielectric characteristics of the low dielectric constant ( ⁇ ) and the low dielectric loss tangent (tan ⁇ ) are shown in the frequency range of 1 to 100 GHz. The reason for this will be described in detail below.
  • the imidazole compound acts as a curing agent or a curing catalyst for the epoxy resin
  • the unshared electron pair of the nitrogen atom at the 3-position of the heterocyclic ring contributes to the curing reaction.
  • a long hydrocarbon chain such as an alkyl group having 5 or more carbon atoms at the 1-position of the heterocyclic ring improves the dielectric characteristics in the high frequency region, that is, has a low dielectric constant in the frequency region of 1 to 100 GHz. ( ⁇ ) and low dielectric loss tangent (tan ⁇ ).
  • An imidazole compound in which a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring has a frequency of 1 to 100 GHz without impairing the reactivity when acting as a curing agent curing catalyst for an epoxy resin.
  • a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) can be achieved. This point is also apparent from the results of Examples described later.
  • the imidazole compound used in Comparative Example 3 described later has a long hydrocarbon chain as a side chain of the heterocyclic ring. However, the side chain is at the 2-position of the heterocycle.
  • the (C) component imidazole compound is not particularly limited as long as a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring.
  • an imidazole compound represented by the following formula (I) can be used.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • m is 0 or 1.
  • R 4 is an alkylene group having 1 to 3 carbon atoms or —CH 2 CH 2 COO—.
  • R 5 is an alkyl group having 5 to 10 carbon atoms.
  • the imidazole compound as component (C) include the following formulas (I1) to (I4). Only one of these examples of imidazole compounds may be used, or two or more imidazole compounds may be used in combination. Among these, the following formulas (I3) and (I4) are preferable from the viewpoint of a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a 100 GHz region. From the viewpoint of controlling the reactivity, the following formula (I4) is more preferable.
  • the content of the imidazole compound as the component (C) is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass in total of the epoxy resin as the component (A) and the resin as the component (B).
  • the amount is preferably 0.5 to 3.0 parts by mass.
  • the resin composition of the present embodiment can be obtained by dissolving or dispersing a raw material containing the above components (A) to (C) and other components added as necessary in an organic solvent. .
  • other components include inorganic fillers such as silica filler, flame retardants, coupling agents, leveling agents, dispersants, and antifoaming agents.
  • the apparatus for dissolving or dispersing these raw materials As a stirrer provided with a heating device, a dissolver, a planetary mixer, a lyric machine, a three-roll mill, a ball mill, a bead mill, or the like can be used. These devices may be used in combination as appropriate.
  • the cured resin has sufficient adhesive strength.
  • the peel strength (180 degree peel) of the cured resin with respect to the polyimide film measured in accordance with JIS C6481 is preferably 6.5 N / cm or more, more preferably 7.0 N / cm or more, and still more preferably. Is 7.5 N / cm or more.
  • the cured resin has a peel strength (180 degree peel) with respect to the glossy copper foil surface measured according to JIS C6481, preferably 6.5 N / cm or more, more preferably 7.0 N / cm or more, and still more preferably. 7.5 N / cm or more.
  • the cured product of the resin composition of the present embodiment preferably has excellent dielectric properties in a high frequency region.
  • the dielectric constant ( ⁇ ) of the cured product in the frequency region of 1 to 100 GHz is preferably 3.5 or less, more preferably 3.0 or less.
  • the dielectric loss tangent (tan ⁇ ) in the frequency region of 1 to 100 GHz is preferably 0.010 or less, more preferably 0.0095 or less.
  • thermosetting film of the present embodiment is formed from the above resin composition. Specifically, the thermosetting film is obtained by drying a resin composition applied on at least one surface of a desired support.
  • a support body the support body which has a desired form according to the manufacturing method of a thermosetting film is selected suitably.
  • a specific support is not particularly limited. Examples of the support that can be used include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene.
  • the support is preferably subjected to a release treatment with a release agent such as a silicone compound.
  • the method for applying the resin composition to the support is not particularly limited.
  • a preferable method is a micro gravure method, a slot die method, or a doctor blade method from the viewpoint of thinning and controlling the film thickness.
  • a film having a thickness of, for example, 5 to 500 ⁇ m5 can be obtained by the slot die method.
  • Drying conditions can be appropriately set according to the type of organic solvent used in the resin composition, the amount thereof, the thickness of coating, and the like.
  • the drying can be performed at 50 to 120 ° C. for about 1 to 30 minutes.
  • the film may be peeled from the support at a desired timing.
  • the film obtained by the above procedure can be thermally cured at a temperature of 130 ° C. or higher and 250 ° C. or lower, preferably 150 ° C. or higher and 200 ° C. or lower for 30 to 180 minutes.
  • the resin composition is preferably press-cured under the above-mentioned curing conditions.
  • the thickness of the film obtained by the above procedure is preferably 5 ⁇ m or more and 200 ⁇ m or less. When the thickness of the film is less than 5 ⁇ m, required film characteristics such as insulation may not be obtained.
  • the thickness of the film is more preferably 15 ⁇ m to 150 ⁇ m, and still more preferably 20 ⁇ m to 100 ⁇ m.
  • thermosetting film of the present embodiment in which the cured resin has the characteristics described above is suitable for an adhesive film, an interlayer adhesive film, and a coverlay film for electrical or electronic use.
  • the resin composition of the present disclosure is used for interlayer adhesion of the constituent elements.
  • the resin composition of the present disclosure is used for interlayer adhesion between an electronic component and a substrate.
  • the thermosetting film formed from the resin composition of this embodiment is used in the semiconductor device containing an electronic component.
  • Examples 1 to 11, Comparative Examples 1 to 4 A predetermined amount of each resin (A-1, A-2, A-3, B-1, B-2, B-3, B-4, and B-5) and a predetermined amount in the composition shown in the following table Of toluene was weighed into a container. Subsequently, the mixture of resin and toluene was heated and dissolved using a heating stirrer, and then cooled to room temperature. Subsequently, a predetermined amount of imidazole compound or the like (C-1, C′-1, C′-2, C′-3, and C′-4) was added to the mixture.
  • Example 11 the mixture of the obtained component (A), component (B), and component (C) or (C ′) is rotated or revolved (Mazerustar (trade name), manufactured by Kurashiki Boseki Co., Ltd.). ),
  • the resin composition was prepared by stirring and mixing for 3 minutes.
  • a fused spherical silica filler MP-15EF manufactured by Tatsumori Co., Ltd., average particle size 1.5 ⁇ m
  • Silica filler was dispersed in the resin composition.
  • a coating liquid containing the resin composition was prepared by adjusting the viscosity of the resin composition thus obtained with toluene.
  • Epoxy resin (A-1) Epoxy resin having naphthalene skeleton, HP4032D (trade name), manufactured by DIC Corporation, epoxy equivalents 136 to 148 (A-2); An epoxy resin having an anthracene skeleton, JERYX8800 (trade name), manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 (A-3); and Epoxy resin having biphenyl skeleton, NC-3000H (trade name), manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288
  • B-1 Solvent-soluble polyimide resin synthesized by the following procedure: Stirrer, water separator, thermometer, and nitrogen
  • BTDT-UP commercially available aromatic tetracarboxylic dianhydride
  • 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane was charged.
  • the solution in the reaction vessel was heated to 60 ° C.
  • (B-2) Solvent-soluble polyimide resin synthesized by the following procedure: In the same reaction vessel as (B-1), commercially available aromatic tetracarboxylic dianhydride (BTDA-PF (trade name), Evonik Japan Co., Ltd.) 190.0 g, cyclohexanone 912.0 g, and methylcyclohexane 182.4 g were charged. The solution in the reaction vessel was heated to 60 ° C.
  • BTDA-PF aromatic tetracarboxylic dianhydride
  • B-3 Solvent-soluble polyimide resin synthesized by the following procedure (B-1)
  • commercially available aromatic tetracarboxylic dianhydride (BisDA1000 (trade name), manufactured by SABIC Japan Co., Ltd.) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged.
  • the solution in the reaction vessel was heated to 60 ° C.
  • 43.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, manufactured by Croda Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane were added dropwise to the reaction solution.
  • PRIAMINE commercially available dimer diamine
  • Imidazole compound (C-1) Imidazole compound having a structure represented by the following formula, EH-2021 (trade name), manufactured by ADEKA Corporation (C′-1): 1-benzyl-2-phenylimidazole, 1B2PZ (trade name), manufactured by Shikoku Chemicals Co., Ltd. (C′-2): 2-ethyl-4-methylimidazole, 2E4MZ (trade name), Shikoku Kasei Kogyo Co., Ltd. (C'-3): 1-cyanoethyl-2-undecylimidazole, C11ZCN (trade name), Shikoku Kasei Kogyo Co., Ltd. (C'-4): 2-ethylhexyl acrylate, Nacalai Made by Tesque Corporation
  • Upilex registered trademark
  • 12.5CA manufactured by Ube Industries, Ltd.
  • a test piece was obtained by cutting the obtained laminated film containing a cured film into a width of 10 mm.
  • the peel strength of the cured film was measured by peeling each of the two polyimide films of the test piece from the cured film in the opposite direction to each other by autograph. The average value of the values obtained by the five measurements was calculated as the peak intensity measurement value.
  • Dielectric constant ( ⁇ ), dissipation factor (tan ⁇ ) 1. After the uncured film obtained in the above was cured on the substrate surface for 200 ° C. for 60 minutes, the substrate was peeled from the cured film. ⁇ and tan ⁇ of the cured film cut to 130 ⁇ 70 mm were measured by the SPDR method at a dielectric resonance frequency of 2 GHz. The results are shown in the table below.
  • Example 1 In each of Examples 1 to 11, a PI peel strength of 7.0 N / cm or more, a dielectric constant ( ⁇ ) of 3.0 or less, and a dielectric loss tangent (tan ⁇ ) of 0.010 or less were shown.
  • Example 2 and 3 and Example 1 differ in the mixture ratio of the imidazole compound of (C) component.
  • Examples 4 and 5 are different from Example 1 in the type of component (A) epoxy resin.
  • Examples 6 to 9 and Example 1 differ in the type of resin as component (B).
  • Examples 10 to 11 and Example 1 differ in the blending ratio of component (B) to component (A).
  • the silica filler is further used.
  • Comparative Example 1 an imidazole compound having a benzyl group at the 1-position of the heterocyclic ring is used in place of the imidazole compound as the component (C).
  • Comparative Example 2 there is no alkyl group having 5 or more carbon atoms at the 1-position of the heterocyclic ring of the imidazole compound.
  • Comparative Example 3 an imidazole compound having a side chain having an alkyl group having 5 or more carbon atoms at the 2-position of the heterocyclic ring is used in place of the imidazole compound of component (C).
  • Comparative Example 4 a compound corresponding to the thermal decomposition product of the imidazole compound (C-1) used in the examples is blended.
  • the resin composition according to the embodiment of the present disclosure may be the following first to third resin compositions.
  • the first resin composition comprises (A) an epoxy resin, (B) a resin having a dielectric loss tangent (tan ⁇ ) of less than 0.005 in the region of a frequency of 1 to 100 GHz, and (C) the first position of the heterocyclic ring. Including imidazole compounds in which a side chain having a C5 or higher alkyl group is present.
  • the second resin composition is the first resin composition in which the (C) imidazole compound is represented by the following formula (I).
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is 0 or 1, and R 4 is An alkylene group having 1 to 3 carbon atoms or a group: —CH 2 CH 2 COO—, and R 5 represents an alkyl group having 5 to 10 carbon atoms.
  • the (B) resin is at least one selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. 1 or 2 resin composition.
  • the thermosetting film according to the embodiment of the present disclosure may be formed of any one of the first to third resin compositions.
  • the cured resin according to the embodiment of the present disclosure may be any one of the first to third resin compositions or a cured resin obtained by curing the thermosetting film.
  • the laminated board which concerns on embodiment of this indication may be a laminated board containing the said resin hardened
  • the printed wiring board according to the embodiment of the present disclosure may be a printed wiring board including the resin cured product.
  • the semiconductor device according to the embodiment of the present disclosure may be a semiconductor device including the cured resin.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne : un film thermodurcissable qui présente une excellente force de liaison à une feuille métallique contenue dans des lignes de câblage d'une carte de circuit imprimé et un matériau de substrat tel qu'un polyimide, tout en présentant des caractéristiques diélectriques dans une région haute fréquence, en particulier, une faible constante diélectrique (ε) et une tangente de perte diélectrique (tan δ) faible dans une région de fréquence de 1 à 100 GHz ; et une composition de résine qui est utilisée pour la production de ce film thermodurcissable. L'invention concerne une composition de résine qui contient (A) une résine époxy, (B) une résine qui présente une tangente de perte diélectrique (tan δ) inférieure à 0,005 dans une région de fréquence de 1 à 100 GHz et (C) un composé imidazole dans lequel une chaîne latérale ayant un groupe alkyle contenant 5 atomes de carbone ou plus est présente en position 1 d'un hétérocycle.
PCT/JP2017/041129 2016-11-24 2017-11-15 Composition de résine, film thermodurcissable l'utilisant, produit de résine durcie, stratifié, carte de circuit imprimé et dispositif semiconducteur WO2018097010A1 (fr)

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JP2018552527A JP6917636B2 (ja) 2016-11-24 2017-11-15 樹脂組成物、それを用いた熱硬化性フィルム、樹脂硬化物、積層板、プリント配線板、および半導体装置
KR1020197013775A KR102399159B1 (ko) 2016-11-24 2017-11-15 수지 조성물, 이를 사용한 열경화성 필름, 수지 경화물, 적층판, 프린트 배선판 및 반도체 장치
CN201780068677.0A CN109923176B (zh) 2016-11-24 2017-11-15 树脂组合物、使用其的热固性膜、树脂固化物、层叠板、印刷电路板及半导体装置

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WO2020071153A1 (fr) * 2018-10-02 2020-04-09 ナミックス株式会社 Composition de résine, film fixé à un substrat, corps stratifié métal/résine et dispositif semi-conducteur
US20200231786A1 (en) * 2017-10-10 2020-07-23 Ajinomoto Co., Inc. Cured product and production method of same, and resin sheet and resin composition
JP7364243B2 (ja) 2018-12-04 2023-10-18 ナミックス株式会社 ミリ波基板用樹脂組成物、ミリ波基板用接着フィルム、ミリ波基板、ミリ波レーダー基板および半導体装置
JP7474064B2 (ja) 2019-02-18 2024-04-24 積水化学工業株式会社 樹脂材料及び多層プリント配線板

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CN113025117A (zh) * 2020-08-20 2021-06-25 深圳市百柔新材料技术有限公司 阻焊油墨及制备方法和使用方法、印制电路板

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US20200231786A1 (en) * 2017-10-10 2020-07-23 Ajinomoto Co., Inc. Cured product and production method of same, and resin sheet and resin composition
WO2020071153A1 (fr) * 2018-10-02 2020-04-09 ナミックス株式会社 Composition de résine, film fixé à un substrat, corps stratifié métal/résine et dispositif semi-conducteur
WO2020071154A1 (fr) * 2018-10-02 2020-04-09 ナミックス株式会社 Composition de résine, film, feuille stratifiée et dispositif semi-conducteur
CN112771110A (zh) * 2018-10-02 2021-05-07 纳美仕有限公司 树脂组合物、膜、层压板及半导体装置
JPWO2020071153A1 (ja) * 2018-10-02 2021-09-02 ナミックス株式会社 樹脂組成物、基材付フィルム、金属／樹脂積層体および半導体装置
JPWO2020071154A1 (ja) * 2018-10-02 2021-09-24 ナミックス株式会社 樹脂組成物、フィルム、積層板および半導体装置
CN112771110B (zh) * 2018-10-02 2022-11-04 纳美仕有限公司 树脂组合物、膜、层压板及半导体装置
JP7202691B2 (ja) 2018-10-02 2023-01-12 ナミックス株式会社 樹脂組成物、フィルム、積層板および半導体装置
JP7202690B2 (ja) 2018-10-02 2023-01-12 ナミックス株式会社 樹脂組成物、基材付フィルム、金属／樹脂積層体および半導体装置
JP7364243B2 (ja) 2018-12-04 2023-10-18 ナミックス株式会社 ミリ波基板用樹脂組成物、ミリ波基板用接着フィルム、ミリ波基板、ミリ波レーダー基板および半導体装置
JP7474064B2 (ja) 2019-02-18 2024-04-24 積水化学工業株式会社 樹脂材料及び多層プリント配線板

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CN109923176A (zh) 2019-06-21
JPWO2018097010A1 (ja) 2019-10-17
TW201823350A (zh) 2018-07-01
TWI743251B (zh) 2021-10-21
KR102399159B1 (ko) 2022-05-17
JP6917636B2 (ja) 2021-08-11

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