WO2023047901A1 - Non-photosensitive insulation film-forming composition - Google Patents

Non-photosensitive insulation film-forming composition Download PDF

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Publication number
WO2023047901A1
WO2023047901A1 PCT/JP2022/032691 JP2022032691W WO2023047901A1 WO 2023047901 A1 WO2023047901 A1 WO 2023047901A1 JP 2022032691 W JP2022032691 W JP 2022032691W WO 2023047901 A1 WO2023047901 A1 WO 2023047901A1
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group
insulating film
composition
photosensitive insulating
forming
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PCT/JP2022/032691
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French (fr)
Japanese (ja)
Inventor
峻 菅原
勲 安達
圭介 首藤
和宏 澤田
雅久 遠藤
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日産化学株式会社
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Publication of WO2023047901A1 publication Critical patent/WO2023047901A1/en

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols

Definitions

  • the present invention relates to a non-photosensitive insulating film-forming composition and a non-photosensitive resin film obtained from the composition.
  • thermosetting resin that uses a cyanate ester compound and a bismaleimide compound together (for example, Patent Document 1) is called "BT resin", and has excellent workability, heat resistance, and electrical properties. It is widely used as an insulating material for high-performance printed wiring boards.
  • BT resins are required to have a low dielectric constant and a low dielectric loss tangent in order to cope with higher transmission frequencies.
  • Patent Document 2 a thermosetting resin composition containing a BT resin, a cyclic olefin resin having a glass transition temperature of 260 ° C. or more and 310 ° C. or less, and a curing catalyst is used to achieve a low dielectric constant. According to the company, it solved the problems of reducing the dielectric loss tangent.
  • the present invention provides a non-photosensitive insulating film-forming composition capable of achieving a low dielectric constant and a low dielectric loss tangent without being bound by the BT resin, and a non-photosensitive resin film obtained from the composition.
  • the task is to
  • the inventors of the present invention have made intensive studies to achieve the above problems, and found that a polymer having a repeating unit structure containing a specific aromatic heterocycle and a crosslinkable substituent can be used to achieve a low dielectric constant. found that a non-photosensitive resin composition that gives a cured film with a low dielectric loss tangent can be obtained, and completed the present invention.
  • the present invention includes the following.
  • n 1 and n 2 are each independently a number of 0 or more and 1 or less
  • m 1 and m 2 are each independently a number of 0 or more and 1 or less
  • n is a number of 1 or more
  • m is a number of 0 or more, 10 ⁇ n + m ⁇ 500
  • a non-photosensitive insulating film-forming composition comprising a polymer having a repeating unit structure represented by and a solvent.
  • Group A 1 is Represents an aromatic heterocycle represented by the aromatic heterocycle may have a crosslinkable substituent, The composition for forming a non-photosensitive insulating film according to any one of [1] to [3].
  • Group A2 is as well as Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by any of these aromatic heterocycles may have a crosslinkable substituent, The composition for forming a non-photosensitive insulating film according to any one of [1] to [4].
  • Group B 1 is at least one selected from the following, (In the formula, G represents either a direct bond or the following formula. L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. ) The non-photosensitive insulating film-forming composition according to any one of [1] to [5].
  • Group B 1 is The non-photosensitive insulating film-forming composition according to any one of [1] to [6] represented by [8]
  • Group B2 is at least one selected from the following: (In the formula, G represents either a direct bond or the following formula. L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. ) The non-photosensitive insulating film-forming composition according to any one of [1] to [7].
  • Group B2 is at least one selected from the following: (In the formula, G1 and G2 each independently represent either a direct bond or the following formula.
  • L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms.
  • the crosslinkable substituent contains a (meth)acrylate group, a maleimide group, or an allyl group.
  • non-photosensitive resin composition that gives a cured product with a low dielectric constant and a low dielectric loss tangent, and a non-photosensitive resin film obtained from the composition.
  • Non-photosensitive insulating film-forming composition The non-photosensitive insulating film-forming composition of the present invention is Formula (1) below: [In formula (1), Group A 1 is represents a 5- to 8-membered aromatic heterocycle represented by The aromatic heterocycle may have a crosslinkable substituent, Group A2 is represents a 5- to 8-membered aromatic heterocycle represented by The aromatic heterocycle may have a crosslinkable substituent, Group B 1 represents an organic group having 6 to 40 carbon atoms and having a crosslinkable substituent which may contain at least one heteroatom selected from N, S and O and may contain a halogen atom, the group B2 represents an organic group having 6 to 40 carbon atoms which may contain at least one heteroatom selected from N, S and O and which may contain a halogen atom and which has no bridging substituents; n 1 and n 2 are each independently a number of 0 or more and 1 or less, m 1 and m 2 are each independently a number of 0 or more and 1 or less,
  • non-photosensitive in the non-photosensitive insulating film-forming composition means a composition that does not contain a photopolymerization initiator. Each component is described in turn below.
  • the polymer according to the present invention has a repeating unit structure represented by formula (1) above.
  • the group A 1 represents a 5- to 8-membered heteroaromatic ring containing no heteroatoms in the shortest series of covalent bonds between the two bonds, said heteroaromatic ring having a bridging substituent good too.
  • the group A 1 is represents an aromatic heterocycle represented by the aromatic heterocycle may have a crosslinkable substituent.
  • Group A1 may be one or a combination of two or more.
  • the group A2 represents a 5- to 8-membered aromatic heterocycle containing a nitrogen atom in the shortest series of covalent bonds between the two bonds, the aromatic heterocycle being bridging It may have a substituent.
  • the group A2 is as well as represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by and any of these aromatic heterocycles may have a crosslinkable substituent.
  • Group A2 may be one or a combination of two or more.
  • the crosslinkable substituent includes a radical crosslinkable group.
  • the crosslinkable substituent contains a (meth)acrylate group, a maleimide group, or an allyl group.
  • crosslinkable substituent containing a (meth)acrylate group the following general formula (2): (wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * is It is a bonding site with group A 1 , group A 2 or group B 1 in general formula (1).).
  • R 3 in the general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but from the viewpoint of radical reaction reactivity, it is a hydrogen atom or a methyl group. is preferred.
  • R 4 and R 5 in the general formula (2) are not particularly limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably a hydrogen atom.
  • n in the general formula (2) is an integer of 1 or more and 10 or less, preferably 1 or more and 4 or less.
  • monovalent organic groups having 1 to 3 carbon atoms include linear alkyl groups such as methyl group, ethyl group and propyl group; branched alkyl groups such as isopropyl group; Cyclic alkyl group; alkenyl group such as vinyl group and allyl group; alkynyl group such as ethynyl group; alkoxy group such as methoxy group, ethoxy group and propoxy group; acyl group such as acetyl group; ester group such as methoxycarbonyl group; carbamoyl group; cyano group; oxiranyl group, aziridinyl group, thietanyl group, triazinyl group, oxathiolanyl group, azetidinyl group, thiazolinyl group and other heterocyclic groups.
  • the group B 1 may contain at least one heteroatom selected from N, S and O, may contain a halogen atom, and has a crosslinkable substituent having 6 to 40 carbon atoms represents an organic group.
  • the group B 1 is at least one selected from (In the formula, G represents either a direct bond or the following formula.
  • L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
  • the group B 1 is is represented by
  • the group B 2 may contain at least one heteroatom selected from N, S and O, may contain a halogen atom, and has 6 carbon atoms without a crosslinkable substituent. to 40 organic groups.
  • the group B2 is at least one selected from (In the formula, G represents either a direct bond or the following formula.
  • L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms).
  • the group B2 is preferably at least one selected from the following.
  • G1 and G2 each independently represent either a direct bond or the following formula.
  • L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms.
  • a polymer having a repeating unit structure represented by formula (1) can be prepared by a known method. For example, a compound represented by XA 1 -X, a compound represented by XA 2 -X, a compound represented by HO-B 1 -OH, and a compound represented by HO-B 2 -OH (Wherein, A 1 , A 2 , B 1 , and B 2 are as defined above, and X is a halogen atom).
  • a compound represented by XA 1 -X, a compound represented by XA 2 -X, a compound represented by HO-B 1 -OH, and a compound represented by HO-B 2 -OH may be used alone or in combination of two or more.
  • the compound represented by HO-B 1 -OH and HO The total amount of the compounds represented by -B 2 -OH can be usually set to 0.1 to 10 mol, preferably 0.1 to 2 mol.
  • a basic or acidic catalyst can be used, but a basic catalyst is preferably used.
  • Basic catalysts include solid base catalysts such as calcium hydroxide, strontium hydroxide octahydrate, barium hydroxide octahydrate, magnesium hydroxide, sodium carbonate and potassium carbonate.
  • acidic catalysts include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate and methanesulfonic acid, formic acid, oxalic acid and the like. carboxylic acids can be used.
  • the amount of the catalyst used varies depending on the type of catalyst used, but is usually 0.00 per 100 parts by mass of the compound represented by XA 1 -X and the compound represented by XA 2 -X. 001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, more preferably 0.05 to 100 parts by mass.
  • the condensation reaction can be carried out without a solvent, but it is usually carried out using a solvent.
  • the solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane, N,N-dimethylacetamide, etc. are mentioned.
  • the condensation reaction temperature is generally 40°C to 200°C, preferably 50°C to 180°C.
  • the reaction time varies depending on the reaction temperature, it is generally 5 minutes to 500 hours, preferably 5 minutes to 200 hours.
  • the weight average molecular weight of the polymer having a repeating unit structure represented by formula (1) is usually 500 to 100,000, preferably 600 to 80,000, 800 to 60,000, or 1,000 to 50,000. be.
  • solvent it is preferable to use an organic solvent from the viewpoint of solubility for the polymer having the repeating unit structure represented by formula (1).
  • an organic solvent from the viewpoint of solubility for the polymer having the repeating unit structure represented by formula (1).
  • the solvent is, for example, 30 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). It can be used in the range of 1500 parts by mass, preferably in the range of 40 to 1000 parts by mass, more preferably in the range of 50 to 300 parts by mass.
  • the non-photosensitive insulating film-forming composition may further contain components other than the polymer having the repeating unit structure represented by formula (1) above and the solvent.
  • Other components include, for example, resin components other than the polymer having the repeating unit structure represented by formula (1), thermal polymerization initiators, hindered phenol compounds, cross-linking agents, fillers, and the like.
  • the non-photosensitive insulating film-forming composition may further contain a resin component other than the polymer having the repeating unit structure represented by formula (1).
  • resin components that can be contained in the non-photosensitive insulating film-forming composition include polyimide, polyoxazole, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.
  • the blending amount of the resin component is preferably in the range of 0.01 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). is.
  • thermal polymerization initiator can be added to the non-photosensitive insulating film-forming composition in order to accelerate thermal polymerization and enhance curability.
  • thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert- butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl Peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-
  • the amount of the thermal polymerization initiator is preferably 1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). Department.
  • a cross-linking agent can be added to the non-photosensitive insulating film-forming composition in order to increase the cross-linking density and curability.
  • a cross-linking agent a polyfunctional vinyl ether compound, a polyfunctional allyl ether compound, and a bismaleimide compound, which undergo a radical polymerization reaction with a thermal polymerization initiator, are preferred.
  • polyfunctional vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether.
  • vinyl ether trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, polyethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, Vinylbenzyl ether, pentaerythritol tetravinyl ether, 4-methoxyvinylbenzyl ether, 2-methoxyvinylbenzyl ether, 1,4-divinyloxymethylbenzene, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether,
  • polyfunctional allyl ether compounds include ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, and bisphenol F alkylene oxide.
  • diallyl ether trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, polyethylene glycol diallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, allylbenzyl ether, pentaerythritol tetraallyl ether, 4-methoxyallylbenzyl ether, 2-methoxyallylbenzyl ether, 1,4-diallyloxymethylbenzene, ethylene oxide-added trimethylolpropane triallyl ether, Examples include, but are not limited to, ethylene oxide-added ditrimethylolpropane tetraallyl ether,
  • bismaleimide compounds include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3′-dimethyl-5,5 '-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis (4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-(4) -maleimidophenoxy)phenyl)sulfone, 4,4′-bis(3-
  • the amount of the cross-linking agent is preferably 1 part by mass to 200 parts by mass, more preferably 1 part by mass to 100 parts by mass, with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). be.
  • fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.
  • a hindered phenol compound can optionally be added to the non-photosensitive insulating film-forming composition as a polymerization inhibitor for the radical cross-linking site.
  • Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-
  • 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.
  • the amount of the hindered phenol compound is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). From the viewpoint of , it is more preferably 0.5 parts by mass to 10 parts by mass.
  • the amount of the hindered phenol compound per 100 parts by mass of the polymer having the repeating unit structure represented by formula (1) is 0.1 part by mass or more, for example, undesirable radical cross-linking reaction in the solution is prevented, On the other hand, when it is 20 parts by mass or less, it is preferable for the cross-linking reaction.
  • non-photosensitive insulating film-forming composition of the present invention is also useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. is.
  • composition for forming a non-photosensitive insulating film of the present invention will be described below using the following examples, but the present invention is not limited thereto.
  • the weight average molecular weights shown in the synthesis examples below in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification).
  • the apparatus, measurement conditions, etc. used for the measurement are as follows.
  • Apparatus GPC system manufactured by JASCO Corporation Column: Shodex (registered trademark) KF-804L and KF-803L Column oven: 40°C Flow rate: 1 mL/min
  • Eluent Tetrahydrofuran Sample concentration: 10 mg/mL
  • Sample injection volume 20 ⁇ L
  • Reference material Monodisperse polystyrene Detector: Differential refractometer
  • n is a number of 1 or more, and 10 ⁇ n ⁇ 500.
  • the resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 819.83 g of methanol and 1168.00 g of pure water to precipitate a polymer.
  • the obtained precipitate was separated by filtration, washed twice with 130.60 g of methanol, and dried in a vacuum to obtain a polymer.
  • Mw weight average molecular weight
  • This polymer has a repeating unit structure represented by the following formula (4).
  • reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 667.22 g of methanol and 911.75 g of pure water to precipitate a polymer.
  • the obtained precipitate was separated by filtration, washed twice with 104.20 g of methanol, and dried under vacuum to obtain a polymer.
  • the resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 146.46 g of methanol and 208.11 g of pure water to precipitate a polymer.
  • the obtained precipitate was separated by filtration, washed twice with 11.82 g of methanol, and dried in a vacuum to obtain a polymer.
  • Mw weight average molecular weight
  • the resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 151.14 g of methanol and 216.36 g of pure water to precipitate a polymer.
  • the obtained precipitate was separated by filtration, washed twice with 11.92 g of methanol, and dried in a vacuum to obtain a polymer.
  • Mw weight average molecular weight
  • This polymer has a repeating unit structure represented by the following formula (7).
  • This polymer has a repeating unit structure represented by the following formula (8).
  • the resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 116.2 g of methanol and 116.3 g of pure water to precipitate a polymer.
  • the obtained precipitate was separated by filtration, washed twice with 18.2 g of methanol, and dried in a vacuum to obtain a polymer.
  • Mw weight average molecular weight
  • n is a number of 1 or more, and 10 ⁇ n ⁇ 500.
  • the resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solvent of 452.1 g of methanol and 452.1 g of pure water to precipitate the polymer. rice field.
  • the obtained precipitate was separated by filtration, washed twice with 72.3 g of methanol, and dried in a vacuum to obtain a polymer.
  • Mw weight average molecular weight
  • Example 1 18.96 g of cyclohexanone was added to 6.32 g of polymer (3) obtained in Synthesis Example 1, 6.32 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Thereafter, the mixture was filtered using a polytetrafluoroethylene (hereinafter abbreviated as PTFE in this specification) microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • PTFE polytetrafluoroethylene
  • Example 2 > 15.80 g of the polymer (4) obtained in Synthesis Example 2, 15.80 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 47.39 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 3 18.96 g of cyclohexanone was added to 6.32 g of the polymer (5) obtained in Synthesis Example 3 and 6.32 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 4 2.53 g of the polymer (6) obtained in Synthesis Example 4, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 5 2.53 g of the polymer (7) obtained in Synthesis Example 5, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 6 2.53 g of the polymer (8) obtained in Synthesis Example 6, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 7 2.53 g of the polymer (9) obtained in Synthesis Example 7, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 8 > 4.21 g of the polymer (10) obtained in Synthesis Example 8, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 9 7.58 g of cyclohexanone was added to 4.21 g of polymer (11) obtained in Synthesis Example 9, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 10 9.48 g of cyclohexanone was added to 4.25 g of the polymer (12) obtained in Synthesis Example 10 and 0.85 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I. Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 11 A composition was prepared by dissolving 4.74 g of the polymer (3) obtained in Synthesis Example 1 in 7.11 g of cyclohexanone. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 12 A composition was prepared by dissolving 7.58 g of polymer (4) obtained in Synthesis Example 2 in 15.16 g of cyclohexanone. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 13 4.21 g of the polymer (3) obtained in Synthesis Example 1, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 14 7.58 g of cyclohexanone was added to 4.21 g of the polymer (4) obtained in Synthesis Example 2, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 15 9.48 g of cyclohexanone was added to 5.05 g of the polymer (4) obtained in Synthesis Example 2 and 1.26 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 16 3.79 g of the polymer (4) obtained in Synthesis Example 2, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.) was added to 9.48 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • Example 17 9.48 g of cyclohexanone was added to 2.53 g of the polymer (4) obtained in Synthesis Example 2 and 3.79 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 ⁇ m to prepare a non-photosensitive resin composition.
  • ⁇ Comparative Example 1> Dissolve 9.00 g of 2,2-bis(4-cyanatophenyl)propane and 1.00 g of 4,4'-bismaleimidophenylmethane in 10.00 g of tetrahydrofuran, and further dissolve 0.10 g of iron acetylacetone as a curing catalyst. to prepare a solution.
  • the prepared solution was applied using a spin coater onto an aluminum foil laminated on a silicon wafer, prebaked at 75°C for 5 minutes, and further baked at 100°C for 1 hour and then at 160°C for 4 hours under vacuum to obtain a thick layer.
  • a BT resin film having a thickness of about 10 to 30 ⁇ m was formed.
  • the non-photosensitive resin composition prepared in Examples 1 to 17 was applied using a spin coater onto an aluminum foil laminated on a silicon wafer, prebaked at 100 ° C. for 5 minutes, and further baked at 230 ° C. for 4 minutes under nitrogen. It was baked for a period of time to form a film having a thickness of about 10-20 ⁇ m. After that, it was immersed in 6N hydrochloric acid. Aluminum was dissolved, and the part where the film floated was recovered and cut into a length of 7.5 cm and a width of 6.3 cm to obtain a self-supporting film.
  • composition for forming a non-photosensitive insulating film according to the present invention, a cured film exhibiting a low dielectric constant and a low dielectric loss tangent to BT resin is provided.

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Abstract

The present invention provides: a non-photosensitive insulation film-forming composition capable of achieving a low dielectric constant and a low dielectric loss tangent; and a non-photosensitive resin film obtained from said composition.　This non-photosensitive insulation film-forming composition contains a solvent and a polymer that has a repeating unit structure represented by formula (1). (In formula (1), group A1 represents an aromatic heterocycle represented by (AA); group A2 represents an aromatic heterocycle represented by (BB); group A1 and group A2 may have crosslinkable substituents; group B1 represents an organic group having a crosslinkable substituent; and group B2 represents an organic group not having a crosslinkable substituent.)

Description

非感光性絶縁膜形成組成物Non-photosensitive insulating film-forming composition
　本発明は、非感光性絶縁膜形成組成物、及び該組成物から得られる非感光性樹脂膜に関する。 The present invention relates to a non-photosensitive insulating film-forming composition and a non-photosensitive resin film obtained from the composition.
　シアン酸エステル化合物と、ビスマレイミド化合物とを併用する熱硬化性樹脂（例えば、特許文献１）は「ＢＴレジン」と呼ばれ、加工性、耐熱性、電気特性に優れた熱硬化性樹脂として、高機能のプリント配線基板用材料等の絶縁材料として幅広く使用されている。しかし、近年の通信機器の高速通信化に伴い、伝送周波数の高周波数化に対応するために、ＢＴレジンの低比誘電率化や低誘電正接化が求められている。かかる課題に対して、特許文献２では、ＢＴレジンと、ガラス転移温度が２６０℃以上３１０℃以下である環状オレフィン系樹脂と、硬化触媒とを含む熱硬化性樹脂組成物により、低比誘電率化や低誘電正接化の課題を解決できたとしている。 A thermosetting resin that uses a cyanate ester compound and a bismaleimide compound together (for example, Patent Document 1) is called "BT resin", and has excellent workability, heat resistance, and electrical properties. It is widely used as an insulating material for high-performance printed wiring boards. However, with the recent trend toward high-speed communication in communication equipment, BT resins are required to have a low dielectric constant and a low dielectric loss tangent in order to cope with higher transmission frequencies. In response to this problem, in Patent Document 2, a thermosetting resin composition containing a BT resin, a cyclic olefin resin having a glass transition temperature of 260 ° C. or more and 310 ° C. or less, and a curing catalyst is used to achieve a low dielectric constant. According to the company, it solved the problems of reducing the dielectric loss tangent.
特公昭５４－３０４４０号公報Japanese Patent Publication No. 54-30440 特開２０１７－８８６４７号公報JP 2017-88647 A
　しかし、ＢＴレジンを含む組成物の改良だけでは、電気特性の改善に限界がある。 However, there is a limit to the improvement in electrical properties just by improving the composition containing BT resin.
　従って、本発明は、ＢＴレジンに縛られることなく、低比誘電率化や低誘電正接化を達成できる非感光性絶縁膜形成組成物、及び該組成物から得られる非感光性樹脂膜を提供することを課題とする。 Therefore, the present invention provides a non-photosensitive insulating film-forming composition capable of achieving a low dielectric constant and a low dielectric loss tangent without being bound by the BT resin, and a non-photosensitive resin film obtained from the composition. The task is to
　本発明者らは、上記の課題を達成すべく鋭意検討を重ねた結果、特定の芳香族複素環と架橋性置換基とを含む繰り返し単位構造を有するポリマーを採用することにより、低比誘電率で、低誘電正接の硬化膜を与える非感光性樹脂組成物が得られることを見出し、本発明を完成するに至った。 The inventors of the present invention have made intensive studies to achieve the above problems, and found that a polymer having a repeating unit structure containing a specific aromatic heterocycle and a crosslinkable substituent can be used to achieve a low dielectric constant. found that a non-photosensitive resin composition that gives a cured film with a low dielectric loss tangent can be obtained, and completed the present invention.
　即ち、本発明は以下を包含する。
［１］　下記式（１）：
Figure JPOXMLDOC01-appb-C000015
［式（１）において、
基Ａ１は、
Figure JPOXMLDOC01-appb-C000016
で表される５乃至８員芳香族複素環を表し、
当該芳香族複素環は架橋性置換基を有してもよく、
基Ａ２は、
Figure JPOXMLDOC01-appb-C000017
で表される５乃至８員芳香族複素環を表し、
当該芳香族複素環は架橋性置換基を有してもよく、
基Ｂ１は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有する炭素原子数６乃至４０の有機基を表し、
基Ｂ２は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有さない炭素原子数６乃至４０の有機基を表し、
ｎ１、ｎ２はそれぞれ独立に０以上、１以下の数であり、
ｍ１、ｍ２はそれぞれ独立に０以上、１以下の数であり、
ｎは１以上の数であり、
ｍは０以上の数であり、
１０≦ｎ＋ｍ≦５００であり、
但し、基Ａ１、基Ａ２が共に架橋性置換基を有しないとき、
ｍ≠０であればｎ１及びｍ１の少なくとも一方は１であり、
ｍ＝０であればｎ１は１である。］
で表される繰り返し単位構造を有するポリマー、及び
　溶媒
　を含む非感光性絶縁膜形成組成物。
［２］　架橋剤をさらに含む、［１］に記載の非感光性絶縁膜形成組成物。
［３］　前記架橋剤がビスマレイミド化合物である、［２］に記載の非感光性絶縁膜形成組成物。
［４］　基Ａ１が、
Figure JPOXMLDOC01-appb-C000018
で表される芳香族複素環を表し、当該芳香族複素環は架橋性置換基を有してもよい、
［１］乃至［３］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［５］　基Ａ２が、
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
及び
Figure JPOXMLDOC01-appb-C000021
で表される芳香族複素環からなる群より選択される少なくとも一種の芳香族複素環を表し、これらの芳香族複素環はいずれも架橋性置換基を有してもよい、
［１］乃至［４］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［６］　基Ｂ１が、下記から選択される少なくとも１種である、
Figure JPOXMLDOC01-appb-C000022
（式中、Ｇは直接結合、又は下記式のいずれかを表す。
Figure JPOXMLDOC01-appb-C000023
Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。）
［１］乃至［５］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［７］　基Ｂ１が、
Figure JPOXMLDOC01-appb-C000024
で表される
［１］乃至［６］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［８］　基Ｂ２が、下記から選択される少なくとも１種である、
Figure JPOXMLDOC01-appb-C000025
（式中、Ｇは直接結合、又は下記式のいずれかを表す。
Figure JPOXMLDOC01-appb-C000026
Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。）
［１］乃至［７］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［９］　基Ｂ２が、下記から選択される少なくとも１種である、
Figure JPOXMLDOC01-appb-C000027
（式中、Ｇ１及びＧ２はそれぞれ独立に、直接結合、又は下記式のいずれかを表す。
Figure JPOXMLDOC01-appb-C000028
Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。）
［１］乃至［７］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［１０］　架橋性置換基がラジカル架橋性基を含む、［１］乃至［９］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［１１］　架橋性置換基が、（メタ）アクリレート基、マレイミド基、又はアリル基を含む、［１］乃至［１０］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［１２］　ｍ＝０である、［１］乃至［１１］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［１３］　前記溶媒の沸点が、２３０℃以下である、［１］乃至［１２］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［１４］　前記溶媒の沸点が２００℃以下である、［１］乃至［１３］のいずれか一項に記載の非感光性絶縁膜形成組成物。
［１５］　［１］乃至［１４］の何れか１項に記載の非感光性絶縁膜形成組成物の塗布膜の硬化物であることを特徴とする非感光性樹脂膜。
［１６］　誘電正接が０．０１未満である、［１５］に記載の非感光性樹脂膜。 That is, the present invention includes the following.
[1] Formula (1) below:
Figure JPOXMLDOC01-appb-C000015
[In formula (1),
Group A 1 is
Figure JPOXMLDOC01-appb-C000016
represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent,
Group A2 is
Figure JPOXMLDOC01-appb-C000017
represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent,
Group B 1 represents an organic group having 6 to 40 carbon atoms and having a crosslinkable substituent which may contain at least one heteroatom selected from N, S and O and may contain a halogen atom,
Group B2 represents an organic group having 6 to 40 carbon atoms and having no bridging substituents and optionally containing at least one heteroatom selected from N, S and O and optionally containing a halogen atom. ,
n 1 and n 2 are each independently a number of 0 or more and 1 or less,
m 1 and m 2 are each independently a number of 0 or more and 1 or less,
n is a number of 1 or more,
m is a number of 0 or more,
10 ≤ n + m ≤ 500,
However, when both the group A 1 and the group A 2 do not have a crosslinkable substituent,
at least one of n1 and m1 is 1 if m≠0;
n1 is 1 if m=0. ]
A non-photosensitive insulating film-forming composition comprising a polymer having a repeating unit structure represented by and a solvent.
[2] The non-photosensitive insulating film-forming composition according to [1], further comprising a cross-linking agent.
[3] The composition for forming a non-photosensitive insulating film according to [2], wherein the cross-linking agent is a bismaleimide compound.
[4] Group A 1 is
Figure JPOXMLDOC01-appb-C000018
Represents an aromatic heterocycle represented by the aromatic heterocycle may have a crosslinkable substituent,
The composition for forming a non-photosensitive insulating film according to any one of [1] to [3].
[5] Group A2 is
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
as well as
Figure JPOXMLDOC01-appb-C000021
Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by any of these aromatic heterocycles may have a crosslinkable substituent,
The composition for forming a non-photosensitive insulating film according to any one of [1] to [4].
[6] Group B 1 is at least one selected from the following,
Figure JPOXMLDOC01-appb-C000022
(In the formula, G represents either a direct bond or the following formula.
Figure JPOXMLDOC01-appb-C000023
L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
The non-photosensitive insulating film-forming composition according to any one of [1] to [5].
[7] Group B 1 is
Figure JPOXMLDOC01-appb-C000024
The non-photosensitive insulating film-forming composition according to any one of [1] to [6] represented by
[8] Group B2 is at least one selected from the following:
Figure JPOXMLDOC01-appb-C000025
(In the formula, G represents either a direct bond or the following formula.
Figure JPOXMLDOC01-appb-C000026
L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
The non-photosensitive insulating film-forming composition according to any one of [1] to [7].
[9] Group B2 is at least one selected from the following:
Figure JPOXMLDOC01-appb-C000027
(In the formula, G1 and G2 each independently represent either a direct bond or the following formula.
Figure JPOXMLDOC01-appb-C000028
L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
The non-photosensitive insulating film-forming composition according to any one of [1] to [7].
[10] The non-photosensitive insulating film-forming composition according to any one of [1] to [9], wherein the crosslinkable substituent contains a radical crosslinkable group.
[11] The non-photosensitive insulating film-forming composition according to any one of [1] to [10], wherein the crosslinkable substituent contains a (meth)acrylate group, a maleimide group, or an allyl group.
[12] The non-photosensitive insulating film-forming composition according to any one of [1] to [11], wherein m=0.
[13] The composition for forming a non-photosensitive insulating film according to any one of [1] to [12], wherein the boiling point of the solvent is 230°C or lower.
[14] The composition for forming a non-photosensitive insulating film according to any one of [1] to [13], wherein the solvent has a boiling point of 200° C. or lower.
[15] A non-photosensitive resin film which is a cured product of a coating film of the non-photosensitive insulating film-forming composition according to any one of [1] to [14].
[16] The non-photosensitive resin film of [15], which has a dielectric loss tangent of less than 0.01.
　本発明によれば、低比誘電率で、低誘電正接の硬化物を与える非感光性樹脂組成物、該組成物から得られる非感光性樹脂膜を提供することができる。 According to the present invention, it is possible to provide a non-photosensitive resin composition that gives a cured product with a low dielectric constant and a low dielectric loss tangent, and a non-photosensitive resin film obtained from the composition.
［非感光性絶縁膜形成組成物］
　本発明の非感光性絶縁膜形成組成物は、
　下記式（１）：
Figure JPOXMLDOC01-appb-C000029
［式（１）において、
基Ａ１は、
Figure JPOXMLDOC01-appb-C000030
で表される５乃至８員芳香族複素環を表し、
当該芳香族複素環は架橋性置換基を有してもよく、
基Ａ２は、
Figure JPOXMLDOC01-appb-C000031
で表される５乃至８員芳香族複素環を表し、
当該芳香族複素環は架橋性置換基を有してもよく、
基Ｂ１は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有する炭素原子数６乃至４０の有機基を表し、
基Ｂ２は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい架橋性置換基を有さない炭素原子数６乃至４０の有機基を表し、
ｎ１、ｎ２はそれぞれ独立に０以上、１以下の数であり、
ｍ１、ｍ２はそれぞれ独立に０以上、１以下の数であり、
ｎは１以上の数であり、
ｍは０以上の数であり、
１０≦ｎ＋ｍ≦５００であり、
但し、基Ａ１、基Ａ２が共に架橋性置換基を有しないとき、
ｍ≠０であればｎ１及びｍ１の少なくとも一方は１であり、
ｍ＝０であればｎ１は１である。］
で表される繰り返し単位構造を有するポリマー、及び
溶媒
を含む。
　ここで、非感光性絶縁膜形成組成物にいう「非感光性」とは、光重合開始剤を含まない組成物を意味する。
　各成分を以下に順に説明する。 [Non-photosensitive insulating film-forming composition]
The non-photosensitive insulating film-forming composition of the present invention is
Formula (1) below:
Figure JPOXMLDOC01-appb-C000029
[In formula (1),
Group A 1 is
Figure JPOXMLDOC01-appb-C000030
represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent,
Group A2 is
Figure JPOXMLDOC01-appb-C000031
represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent,
Group B 1 represents an organic group having 6 to 40 carbon atoms and having a crosslinkable substituent which may contain at least one heteroatom selected from N, S and O and may contain a halogen atom,
the group B2 represents an organic group having 6 to 40 carbon atoms which may contain at least one heteroatom selected from N, S and O and which may contain a halogen atom and which has no bridging substituents;
n 1 and n 2 are each independently a number of 0 or more and 1 or less,
m 1 and m 2 are each independently a number of 0 or more and 1 or less,
n is a number of 1 or more,
m is a number of 0 or more,
10≦n+m≦500,
However, when both the group A 1 and the group A 2 do not have a crosslinkable substituent,
at least one of n1 and m1 is 1 if m≠0;
n1 is 1 if m=0. ]
Including a polymer having a repeating unit structure represented by and a solvent.
Here, "non-photosensitive" in the non-photosensitive insulating film-forming composition means a composition that does not contain a photopolymerization initiator.
Each component is described in turn below.
＜ポリマー＞
　本発明に係るポリマーは、上記式（１）で表される繰り返し単位構造を有する。 <Polymer>
The polymer according to the present invention has a repeating unit structure represented by formula (1) above.
　基Ａ１は、二つの結合手の間の最短の一連の共有結合中にヘテロ原子を含まない５乃至８員芳香族複素環を表し、当該芳香族複素環は架橋性置換基を有してもよい。 The group A 1 represents a 5- to 8-membered heteroaromatic ring containing no heteroatoms in the shortest series of covalent bonds between the two bonds, said heteroaromatic ring having a bridging substituent good too.
　好ましくは、基Ａ１は、
Figure JPOXMLDOC01-appb-C000032
で表される芳香族複素環を表し、当該芳香族複素環は架橋性置換基を有してもよい。 Preferably, the group A 1 is
Figure JPOXMLDOC01-appb-C000032
represents an aromatic heterocycle represented by the aromatic heterocycle may have a crosslinkable substituent.
　基Ａ１は１種でも２種以上の組み合わせでもよい。 Group A1 may be one or a combination of two or more.
　上記式（１）において、基Ａ２は、二つの結合手の間の最短の一連の共有結合中に窒素原子を含む５乃至８員芳香族複素環を表し、当該芳香族複素環は架橋性置換基を有してもよい。 In the above formula (1), the group A2 represents a 5- to 8-membered aromatic heterocycle containing a nitrogen atom in the shortest series of covalent bonds between the two bonds, the aromatic heterocycle being bridging It may have a substituent.
　好ましくは、基Ａ２は、
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
及び
Figure JPOXMLDOC01-appb-C000035
で表される芳香族複素環からなる群より選択される少なくとも一種の芳香族複素環を表し、これらの芳香族複素環はいずれも架橋性置換基を有してもよい。 Preferably, the group A2 is
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
as well as
Figure JPOXMLDOC01-appb-C000035
represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by and any of these aromatic heterocycles may have a crosslinkable substituent.
　基Ａ２は１種でも２種以上の組み合わせでもよい。 Group A2 may be one or a combination of two or more.
　好ましくは、架橋性置換基はラジカル架橋性基を含む。 Preferably, the crosslinkable substituent includes a radical crosslinkable group.
　好ましくは、架橋性置換基は、（メタ）アクリレート基、マレイミド基、又はアリル基を含む。 Preferably, the crosslinkable substituent contains a (meth)acrylate group, a maleimide group, or an allyl group.
（メタ）アクリレート基を含む架橋性置換基としては、下記一般式（２）：
Figure JPOXMLDOC01-appb-C000036
（式中、Ｒ３、Ｒ４及びＲ５は、それぞれ独立に、水素原子、又は炭素原子数１～３の１価の有機基であり、ｍは１～１０の整数である。＊は、一般式（１）の基Ａ１、基Ａ２、又は基Ｂ１との結合部位である。）で表される基が挙げられる。 As the crosslinkable substituent containing a (meth)acrylate group, the following general formula (2):
Figure JPOXMLDOC01-appb-C000036
(wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * is It is a bonding site with group A 1 , group A 2 or group B 1 in general formula (1).).
　上記一般式（２）中のＲ３は、水素原子又は炭素原子数１～３の１価の有機基であれば限定されないが、ラジカル反応の反応性の観点から、水素原子又はメチル基であることが好ましい。 R 3 in the general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but from the viewpoint of radical reaction reactivity, it is a hydrogen atom or a methyl group. is preferred.
　上記一般式（２）中のＲ４及びＲ５は、それぞれ独立に、水素原子又は炭素原子数１～３の１価の有機基であれば限定されないが、水素原子であることが好ましい。 R 4 and R 5 in the general formula (2) are not particularly limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably a hydrogen atom.
　上記一般式（２）中のｍは１以上１０以下の整数であり、好ましくは１以上４以下の整数である。 m in the general formula (2) is an integer of 1 or more and 10 or less, preferably 1 or more and 4 or less.
　炭素原子数１～３の１価の有機基の具体例としては、メチル基、エチル基、プロピル基等の直鎖状アルキル基；イソプロピル基等の分岐鎖状アルキル基；シクロプロピル基等の脂環式アルキル基；ビニル基、アリル基等のアルケニル基；エチニル基等のアルキニル基；メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基；アセチル基等のアシル基；メトキシカルボニル基等のエステル基；ホルミル基；ハロホルミル基；カルバモイル基；シアノ基；オキシラニル基、アジリジニル基、チエタニル基、トリアジニル基、オキサチオラニル基、アゼチジニル基（azetidinyl）、チアゾリニル基（thiazolinyl）等の複素環式基等が挙げられる。 Specific examples of monovalent organic groups having 1 to 3 carbon atoms include linear alkyl groups such as methyl group, ethyl group and propyl group; branched alkyl groups such as isopropyl group; Cyclic alkyl group; alkenyl group such as vinyl group and allyl group; alkynyl group such as ethynyl group; alkoxy group such as methoxy group, ethoxy group and propoxy group; acyl group such as acetyl group; ester group such as methoxycarbonyl group; carbamoyl group; cyano group; oxiranyl group, aziridinyl group, thietanyl group, triazinyl group, oxathiolanyl group, azetidinyl group, thiazolinyl group and other heterocyclic groups.
　上記式（１）において、基Ｂ１は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有する炭素原子数６乃至４０の有機基を表す。 In the above formula (1), the group B 1 may contain at least one heteroatom selected from N, S and O, may contain a halogen atom, and has a crosslinkable substituent having 6 to 40 carbon atoms represents an organic group.
　好ましくは、基Ｂ１は、下記から選択される少なくとも１種である、
Figure JPOXMLDOC01-appb-C000037
（式中、Ｇは直接結合、又は下記式のいずれかを表す。
Figure JPOXMLDOC01-appb-C000038
Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。） Preferably, the group B 1 is at least one selected from
Figure JPOXMLDOC01-appb-C000037
(In the formula, G represents either a direct bond or the following formula.
Figure JPOXMLDOC01-appb-C000038
L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
　好ましくは、基Ｂ１は、
Figure JPOXMLDOC01-appb-C000039
で表される。 Preferably, the group B 1 is
Figure JPOXMLDOC01-appb-C000039
is represented by
　上記式（１）において、基Ｂ２は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有さない炭素原子数６乃至４０の有機基を表す。 In the above formula (1), the group B 2 may contain at least one heteroatom selected from N, S and O, may contain a halogen atom, and has 6 carbon atoms without a crosslinkable substituent. to 40 organic groups.
　好ましくは、基Ｂ２は、下記から選択される少なくとも１種である、
Figure JPOXMLDOC01-appb-C000040
（式中、Ｇは直接結合、又は下記式のいずれかを表す。
Figure JPOXMLDOC01-appb-C000041
Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す）。 Preferably, the group B2 is at least one selected from
Figure JPOXMLDOC01-appb-C000040
(In the formula, G represents either a direct bond or the following formula.
Figure JPOXMLDOC01-appb-C000041
L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms).
　また、基Ｂ２は、下記から選択される少なくとも１種であることも好ましい。
Figure JPOXMLDOC01-appb-C000042
（式中、Ｇ１及びＧ２はそれぞれ独立に、直接結合、又は下記式のいずれかを表す。
Figure JPOXMLDOC01-appb-C000043
Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。） Also, the group B2 is preferably at least one selected from the following.
Figure JPOXMLDOC01-appb-C000042
(In the formula, G1 and G2 each independently represent either a direct bond or the following formula.
Figure JPOXMLDOC01-appb-C000043
L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
　基Ａ１、基Ａ２が共に架橋性置換基を有しないとき、ｍ≠０であればｎ１及びｍ１の少なくとも一方は１であり、ｍ＝０であればｎ１は１である。すなわち、式（１）で表される繰り返し単位構造を有するポリマーにおいて、基Ａ１、基Ａ２が共に架橋性置換基を有しない場合であっても、架橋性置換基を有する基Ｂ１が存在する。 When neither group A 1 nor group A 2 has a crosslinkable substituent, at least one of n 1 and m 1 is 1 if m≠0, and n 1 is 1 if m=0. That is, in the polymer having the repeating unit structure represented by formula (1), even when both the group A 1 and the group A 2 do not have a crosslinkable substituent, the group B 1 having a crosslinkable substituent exist.
　式（１）で表される繰り返し単位構造を有するポリマーにおいて、基Ａ２は必ずしも存在する必要はない。その場合は、式（１）においてｍ＝０である。 The group A2 does not necessarily have to be present in the polymer having the repeating unit structure represented by formula (1). In that case, m=0 in equation (1).
［式（１）で表される繰り返し単位構造を有するポリマーの調製方法］
　式（１）で表される繰り返し単位構造を有するポリマーは、公知の方法によって調製することができる。例えば、Ｘ－Ａ１－Ｘで表される化合物、Ｘ－Ａ２－Ｘで表される化合物、ＨＯ－Ｂ１－ＯＨで表される化合物、及びＨＯ－Ｂ２－ＯＨで表される化合物を適宜選択して縮合させることにより調製することができる（式中、Ａ１、Ａ２、Ｂ１、Ｂ２は上記と同義であり、Ｘはハロゲン原子である）。Ｘ－Ａ１－Ｘで表される化合物、及びＸ－Ａ２－Ｘで表される化合物、並びにＨＯ－Ｂ１－ＯＨで表される化合物、及びＨＯ－Ｂ２－ＯＨで表される化合物はそれぞれ１種を用いてもよく、２種以上を組み合わせて用いてもよい。この縮合反応においては、Ｘ－Ａ１－Ｘで表される化合物とＸ－Ａ２－Ｘで表される化合物の合計１モルに対して、ＨＯ－Ｂ１－ＯＨで表される化合物とＨＯ－Ｂ２－ＯＨで表される化合物の合計を通常０．１乃至１０モル、好ましくは０．１乃至２モルの割合に設定して用いることができる。 [Method for Preparing Polymer Having Repeating Unit Structure Represented by Formula (1)]
A polymer having a repeating unit structure represented by formula (1) can be prepared by a known method. For example, a compound represented by XA 1 -X, a compound represented by XA 2 -X, a compound represented by HO-B 1 -OH, and a compound represented by HO-B 2 -OH (Wherein, A 1 , A 2 , B 1 , and B 2 are as defined above, and X is a halogen atom). A compound represented by XA 1 -X, a compound represented by XA 2 -X, a compound represented by HO-B 1 -OH, and a compound represented by HO-B 2 -OH may be used alone or in combination of two or more. In this condensation reaction , the compound represented by HO-B 1 -OH and HO The total amount of the compounds represented by -B 2 -OH can be usually set to 0.1 to 10 mol, preferably 0.1 to 2 mol.
　縮合反応で用いられる触媒としては、塩基性又は酸性の触媒を用いることが出来るが、塩基性の触媒を用いることが好ましい。
　塩基性の触媒としては、固体塩基触媒が挙げられ、例えば水酸化カルシウム、水酸化ストロンチウム八水和物、水酸化バリウム八水和物、水酸化マグネシウム、炭酸ナトリウム、炭酸カリウム等が挙げられる。
　酸性の触媒としては、例えば硫酸、リン酸、過塩素酸等の鉱酸類、ｐ－トルエンスルホン酸、ｐ－トルエンスルホン酸一水和物、メタンスルホン酸等の有機スルホン酸類、蟻酸、シュウ酸等のカルボン酸類を使用することができる。
　触媒の使用量は、使用する触媒の種類によって異なるが、Ｘ－Ａ１－Ｘで表される化合物とＸ－Ａ２－Ｘで表される化合物の合計１００質量部に対して、通常０．００１乃至１０，０００質量部、好ましくは０．０１乃至１，０００質量部、より好ましくは０．０５乃至１００質量部である。 As the catalyst used in the condensation reaction, a basic or acidic catalyst can be used, but a basic catalyst is preferably used.
Basic catalysts include solid base catalysts such as calcium hydroxide, strontium hydroxide octahydrate, barium hydroxide octahydrate, magnesium hydroxide, sodium carbonate and potassium carbonate.
Examples of acidic catalysts include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate and methanesulfonic acid, formic acid, oxalic acid and the like. carboxylic acids can be used.
The amount of the catalyst used varies depending on the type of catalyst used, but is usually 0.00 per 100 parts by mass of the compound represented by XA 1 -X and the compound represented by XA 2 -X. 001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, more preferably 0.05 to 100 parts by mass.
　縮合反応は無溶剤でも行われるが、通常は溶剤を用いて行われる。溶剤としては反応基質を溶解することができ、反応を阻害しないものであれば特に限定されない。例えば、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、１，２－ジメトキシエタン、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、テトラヒドロフラン、ジオキサン、Ｎ，Ｎ－ジメチルアセトアミド等が挙げられる。縮合反応温度は通常４０℃乃至２００℃、好ましくは５０℃乃至１８０℃である。反応時間は反応温度によって異なるが、通常５分乃至５００時間、好ましくは５分乃至２００時間である。 The condensation reaction can be carried out without a solvent, but it is usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane, N,N-dimethylacetamide, etc. are mentioned. The condensation reaction temperature is generally 40°C to 200°C, preferably 50°C to 180°C. Although the reaction time varies depending on the reaction temperature, it is generally 5 minutes to 500 hours, preferably 5 minutes to 200 hours.
　式（１）で表される繰り返し単位構造を有するポリマーの重量平均分子量は、通常５００～１００，０００、好ましくは６００～８０，０００、８００～６０，０００、又は１，０００～５０，０００である。 The weight average molecular weight of the polymer having a repeating unit structure represented by formula (1) is usually 500 to 100,000, preferably 600 to 80,000, 800 to 60,000, or 1,000 to 50,000. be.
［溶媒］
　溶媒としては、式（１）で表される繰り返し単位構造を有するポリマーに対する溶解性の点から、有機溶媒を用いることが好ましい。具体的には、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、シクロペンタノン、シクロヘキサノン、γ－ブチロラクトン、α－アセチル－γ－ブチロラクトン、メチルラクテート、エチルラクテート、テトラメチル尿素、１，３－ジメチル－２－イミダゾリノン、Ｎ－シクロヘキシル－２－ピロリドン、Ｎ－メチル－２－ピロリジノン、トルエン、メチルエチルケトン等が挙げられ、これらは単独又は２種以上の組合せで用いることができる。好ましくは沸点２３０℃以下の溶媒が望ましく、より好ましくは沸点２００℃以下の溶媒が望ましい。 [solvent]
As the solvent, it is preferable to use an organic solvent from the viewpoint of solubility for the polymer having the repeating unit structure represented by formula (1). Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone , α-acetyl-γ-butyrolactone, methyl lactate, ethyl lactate, tetramethyl urea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, N-methyl-2-pyrrolidinone, toluene, methyl ethyl ketone, etc. and these can be used singly or in combination of two or more. A solvent with a boiling point of 230° C. or lower is preferred, and a solvent with a boiling point of 200° C. or lower is more preferred.
　上記溶媒は、非感光性絶縁膜形成組成物の所望の塗布膜厚及び粘度に応じて、式（１）で表される繰り返し単位構造を有するポリマー１００質量部に対し、例えば、３０質量部～１５００質量部の範囲、好ましくは４０質量部～１０００質量部、より好ましくは５０質量部～３００質量部の範囲で用いることができる。 Depending on the desired coating thickness and viscosity of the non-photosensitive insulating film-forming composition, the solvent is, for example, 30 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). It can be used in the range of 1500 parts by mass, preferably in the range of 40 to 1000 parts by mass, more preferably in the range of 50 to 300 parts by mass.
［その他の成分］
　実施の形態では、非感光性絶縁膜形成組成物は、上記式（１）で表される繰り返し単位構造を有するポリマー、溶媒以外の成分をさらに含有してもよい。その他の成分としては、例えば、式（１）で表される繰り返し単位構造を有するポリマー以外の樹脂成分、熱重合開始剤、ヒンダードフェノール化合物、架橋剤、フィラーなどが挙げられる。 [Other ingredients]
In embodiments, the non-photosensitive insulating film-forming composition may further contain components other than the polymer having the repeating unit structure represented by formula (1) above and the solvent. Other components include, for example, resin components other than the polymer having the repeating unit structure represented by formula (1), thermal polymerization initiators, hindered phenol compounds, cross-linking agents, fillers, and the like.
［式（１）で表される繰り返し単位構造を有するポリマー以外の樹脂成分］
　実施の形態では、非感光性絶縁膜形成組成物は、前記式（１）で表される繰り返し単位構造を有するポリマー以外の樹脂成分をさらに含有してもよい。非感光性絶縁膜形成組成物に含有させることができる樹脂成分としては、例えば、ポリイミド、ポリオキサゾール、ポリオキサゾール前駆体、フェノール樹脂、ポリアミド、エポキシ樹脂、シロキサン樹脂、アクリル樹脂等が挙げられる。
　このような樹脂を配合する場合、樹脂成分の配合量は、式（１）で表される繰り返し単位構造を有するポリマー１００質量部に対して、好ましくは０．０１質量部～２０質量部の範囲である。 [Resin component other than polymer having repeating unit structure represented by formula (1)]
In an embodiment, the non-photosensitive insulating film-forming composition may further contain a resin component other than the polymer having the repeating unit structure represented by formula (1). Examples of resin components that can be contained in the non-photosensitive insulating film-forming composition include polyimide, polyoxazole, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.
When such a resin is blended, the blending amount of the resin component is preferably in the range of 0.01 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). is.
［熱重合開始剤］
　実施の形態では、熱重合を促進し硬化性を高めるために、非感光性絶縁膜形成組成物に熱重合開始剤を配合することができる。熱重合開始剤としては、例えば、ケトンパーオキサイド類（メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド等）、ジアシルパーオキサイド類（アセチルパーオキサイド、ベンゾイルパーオキサイド等）、ハイドロパーオキサイド類（過酸化水素、ｔｅｒｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等）、ジアルキルパーオキサイド類（ジ－ｔｅｒｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ジラウロイルパーオキサイド等）、パーオキシケタール類（ジブチルパーオキシシクロヘキサン等）、アルキルパーエステル類（パーオキシネオデカン酸－ｔｅｒｔ－ブチルエステル、パーオキシピバリン酸－ｔｅｒｔ－ブチルエステル、パーオキシ－２－エチルシクロヘキサン酸－ｔｅｒｔ－アミルエステル等）、過硫酸塩類（過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等）、アゾ系化合物（アゾビスイソブチロニトリル、および２，２’－ジ（２－ヒドロキシエチル）アゾビスイソブチロニトリル等）が挙げられるが、これらに限定されない。また、前記熱重合開始剤としては、市販品を使用することができる。このような熱重合開始剤は、１種を単独で使用することもできるし、あるいは２種以上を組み合わせて使用することもできる。 [Thermal polymerization initiator]
In an embodiment, a thermal polymerization initiator can be added to the non-photosensitive insulating film-forming composition in order to accelerate thermal polymerization and enhance curability. Examples of thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert- butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl Peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy-2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate , ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2′-di(2-hydroxyethyl)azobisisobutyronitrile, etc.), but are not limited thereto. Moreover, a commercially available product can be used as the thermal polymerization initiator. Such thermal polymerization initiators can be used singly or in combination of two or more.
　熱重合開始剤の配合量は、式（１）で表される繰り返し単位構造を有するポリマー１００質量部に対し、好ましくは１質量部～１０質量部であり、より好ましくは１質量部～５質量部である。 The amount of the thermal polymerization initiator is preferably 1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). Department.
［架橋剤］
　実施の形態では、架橋密度を上げて硬化性を高めるために、非感光性絶縁膜形成組成物に架橋剤を配合することができる。このような架橋剤としては、熱重合開始剤によりラジカル重合反応する多官能ビニルエーテル化合物、多官能アリルエーテル化合物、及びビスマレイミド化合物が好ましい。
　多官能ビニルエーテル化合物としては、例えば、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、ポリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ブチレングリコールジビニルエーテル、ヘキサンジオールジビニルエーテル、ビスフェノールＡアルキレンオキシドジビニルエーテル、ビスフェノールＦアルキレンオキシドジビニルエーテル、トリメチロールプロパントリビニルエーテル、ジトリメチロールプロパンテトラビニルエーテル、グリセリントリビニルエーテル、ペンタエリスリトールテトラビニルエーテル、ジペンタエリスリトールペンタビニルエーテル、ジペンタエリスリトールヘキサビニルエーテル、ポリエチレングリコールジビニルエーテル、ペンタエリスリトールジビニルエーテル、ペンタエリスリトールトリビニルエーテル、ビニルベンジルエーテル、ペンタエリスリトールテトラビニルエーテル、４－メトキシビニルベンジルエーテル、２－メトキシビニルベンジルエーテル、１，４－ジビニルオキシメチルベンゼン、エチレンオキシド付加トリメチロールプロパントリビニルエーテル、エチレンオキシド付加ジトリメチロールプロパンテトラビニルエーテル、エチレンオキシド付加ペンタエリスリトールテトラビニルエーテル、エチレンオキシド付加ジペンタエリスリトールヘキサビニルエーテル等の化合物を挙げることができるが、これらに限定されない。
　多官能アリルエーテル化合物としては、例えば、エチレングリコールジアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、プロピレングリコールジアリルエーテル、ブチレングリコールジアリルエーテル、ヘキサンジオールジアリルエーテル、ビスフェノールＡアルキレンオキシドジアリルエーテル、ビスフェノールＦアルキレンオキシドジアリルエーテル、トリメチロールプロパントリアリルエーテル、ジトリメチロールプロパンテトラアリルエーテル、グリセリントリアリルエーテル、ペンタエリスリトールテトラアリルエーテル、ジペンタエリスリトールペンタアリルエーテル、ジペンタエリスリトールヘキサアリルエーテル、ポリエチレングリコールジアリルエーテル、ペンタエリスリトールジアリルエーテル、ペンタエリスリトールトリアリルエーテル、アリルベンジルエーテル、ペンタエリスリトールテトラアリルエーテル、４－メトキシアリルベンジルエーテル、２－メトキシアリルベンジルエーテル、１，４－ジアリルオキシメチルベンゼン、エチレンオキシド付加トリメチロールプロパントリアリルエーテル、エチレンオキシド付加ジトリメチロールプロパンテトラアリルエーテル、エチレンオキシド付加ペンタエリスリトールテトラアリルエーテル、エチレンオキシド付加ジペンタエリスリトールヘキサアリルエーテル等の化合物を挙げることができるが、これらに限定されない。
　ビスマレイミド化合物としては、例えば、ビス（４－マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、ビス（４－マレイミドフェニル）エーテル、ビス（４－マレイミドフェニル）スルホン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、ｍ－フェニレンビスマレイミド、２，２－ビス（４－（４－マレイミドフェノキシ）フェニル）プロパン、ビス（４－マレイミドフェニル）スルホン、ビス（４－マレイミドフェニル）スルフィド、ビス（４－マレイミドフェニル）ケトン、２，２－ビス（４－（４－マレイミドフェノキシ）フェニル）プロパン、ビス（４－（４－マレイミドフェノキシ）フェニル）スルホン、４，４’－ビス（３－マレイミドフェノキシ）ビフェニル、１，６－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、等の化合物を挙げることができるが、これらに限定されない。 [Crosslinking agent]
In embodiments, a cross-linking agent can be added to the non-photosensitive insulating film-forming composition in order to increase the cross-linking density and curability. As such a cross-linking agent, a polyfunctional vinyl ether compound, a polyfunctional allyl ether compound, and a bismaleimide compound, which undergo a radical polymerization reaction with a thermal polymerization initiator, are preferred.
Examples of polyfunctional vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. vinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, polyethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, Vinylbenzyl ether, pentaerythritol tetravinyl ether, 4-methoxyvinylbenzyl ether, 2-methoxyvinylbenzyl ether, 1,4-divinyloxymethylbenzene, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added Examples include, but are not limited to, compounds such as pentaerythritol tetravinyl ether and ethylene oxide-added dipentaerythritol hexavinyl ether.
Examples of polyfunctional allyl ether compounds include ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, and bisphenol F alkylene oxide. diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, polyethylene glycol diallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, allylbenzyl ether, pentaerythritol tetraallyl ether, 4-methoxyallylbenzyl ether, 2-methoxyallylbenzyl ether, 1,4-diallyloxymethylbenzene, ethylene oxide-added trimethylolpropane triallyl ether, Examples include, but are not limited to, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether, and the like.
Examples of bismaleimide compounds include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3′-dimethyl-5,5 '-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis (4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-(4) -maleimidophenoxy)phenyl)sulfone, 4,4′-bis(3-maleimidophenoxy)biphenyl, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, etc., It is not limited to these.
　架橋剤の配合量は、式（１）で表される繰り返し単位構造を有するポリマー１００質量部に対し、好ましくは１質量部～２００質量部であり、より好ましくは１質量部～１００質量部である。 The amount of the cross-linking agent is preferably 1 part by mass to 200 parts by mass, more preferably 1 part by mass to 100 parts by mass, with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). be.
［フィラー］
　フィラーとしては、例えば無機フィラーが挙げられ、具体的にはシリカ、窒化アルミ二ウム、窒化ボロン、ジルコニア、アルミナなどのゾルが挙げられる。 [Filler]
Examples of fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.
［ヒンダードフェノール化合物］
　実施の形態では、ラジカル架橋部位の重合禁止剤として、ヒンダードフェノール化合物を任意に非感光性絶縁膜形成組成物に配合することができる。ヒンダードフェノール化合物としては、例えば、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，５－ジ－ｔ－ブチル－ハイドロキノン、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネ－ト、イソオクチル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、４、４’－メチレンビス（２、６－ジ－ｔ－ブチルフェノール）、４，４’－チオ－ビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデン－ビス（３－メチル－６－ｔ－ブチルフェノール）、トリエチレングリコール－ビス〔３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート〕、１，６－ヘキサンジオール－ビス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、２，２－チオ－ジエチレンビス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、Ｎ，Ｎ’－ヘキサメチレンビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマミド）、２，２’－メチレン－ビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレン－ビス（４－エチル－６－ｔ－ブチルフェノール）、ペンタエリスリチル－テトラキス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、トリス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－イソシアヌレイト、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、１，３，５－トリス（３－ヒドロキシ－２，６－ジメチル－４－イソプロピルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｓ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス［４－（１－エチルプロピル）－３－ヒドロキシ－２，６－ジメチルベンジル］－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス［４－トリエチルメチル－３－ヒドロキシ－２，６－ジメチルベンジル］－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（３－ヒドロキシ－２，６－ジメチル－４－フェニルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，５，６－トリメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－５－エチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－６－エチル－３－ヒドロキシ－２－メチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－６－エチル－３－ヒドロキシ－２，５－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－５，６－ジエチル－３－ヒドロキシ－２－メチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２－メチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，５－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス（４－ｔ－ブチル－５－エチル－３－ヒドロキシ－２－メチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン等が挙げられるが、これに限定されるものではない。これらの中でも、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオンが特に好ましい。 [Hindered phenol compound]
In the embodiment, a hindered phenol compound can optionally be added to the non-photosensitive insulating film-forming composition as a polymerization inhibitor for the radical cross-linking site. Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy- hydrocinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl- tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3, 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2, 6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6 -dimethylbenzyl]- 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)- 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6- dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy- 2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3- hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5, 6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t- Butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl- 3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl- 5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, but are not limited thereto. do not have. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.
　ヒンダードフェノール化合物の配合量は、式（１）で表される繰り返し単位構造を有するポリマー１００質量部に対し、０．１質量部～２０質量部であることが好ましく、ラジカル架橋部位の反応性の観点から０．５質量部～１０質量部であることがより好ましい。ヒンダードフェノール化合物の式（１）で表される繰り返し単位構造を有するポリマー１００質量部に対する配合量が０．１質量部以上である場合、例えば溶液中での望まないラジカル架橋反応が防止され、一方、２０質量部以下である場合には架橋反応に好ましい。 The amount of the hindered phenol compound is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1). From the viewpoint of , it is more preferably 0.5 parts by mass to 10 parts by mass. When the amount of the hindered phenol compound per 100 parts by mass of the polymer having the repeating unit structure represented by formula (1) is 0.1 part by mass or more, for example, undesirable radical cross-linking reaction in the solution is prevented, On the other hand, when it is 20 parts by mass or less, it is preferable for the cross-linking reaction.
　本発明の非感光性絶縁膜形成組成物は、半導体装置への適用の他、多層回路の層間絶縁膜、フレキシブル銅張板のカバーコート、ソルダーレジスト膜、及び液晶配向膜等の用途にも有用である。 In addition to application to semiconductor devices, the non-photosensitive insulating film-forming composition of the present invention is also useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. is.
　以下、本発明の非感光性絶縁膜形成組成物の具体例を、下記実施例を用いて説明するが、これによって本発明が限定されるものではない。 Specific examples of the composition for forming a non-photosensitive insulating film of the present invention will be described below using the following examples, but the present invention is not limited thereto.
　本明細書の下記合成例に示す重量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下、本明細書ではＧＰＣと略称する。）による測定結果である。測定に用いた装置及び測定条件等は次のとおりである。
装置：日本分光（株）製ＧＰＣシステム
カラム：Ｓｈｏｄｅｘ（登録商標）ＫＦ－８０４Ｌ及びＫＦ－８０３Ｌ
カラムオーブン：４０℃
流量：１ｍＬ／分
溶離液：テトラヒドロフラン
試料濃度：１０ｍｇ／ｍＬ
試料注入量：２０μＬ
標準物質：単分散ポリスチレン
検出器：示差屈折計 The weight average molecular weights shown in the synthesis examples below in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). The apparatus, measurement conditions, etc. used for the measurement are as follows.
Apparatus: GPC system manufactured by JASCO Corporation Column: Shodex (registered trademark) KF-804L and KF-803L
Column oven: 40°C
Flow rate: 1 mL/min Eluent: Tetrahydrofuran Sample concentration: 10 mg/mL
Sample injection volume: 20 μL
Reference material: Monodisperse polystyrene Detector: Differential refractometer
＜合成例１＞（ポリマー（３）の合成）
　２０００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン５０．００ｇ（０．３２９ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）１１４．５１ｇ（０．３６６ｍｏｌ）、炭酸カリウム１０９．３２ｇ（０．８３９ｍｏｌ）、Ｎ－エチル－２－ピロリドン５４８．７１ｇを入れて１００℃に昇温し４２時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン３８２．８０ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール３２４１．８１ｇと純水６４８．３６ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール２５９．３５ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は１３，９６８であり、収率は７１．９１％であった。このポリマーは、下記式（３）で表される繰り返し単位構造を有する。 <Synthesis Example 1> (Synthesis of polymer (3))
50.00 g (0.329 mol) of 4,6-dichloropyrimidine and 114.51 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Kagaku Kogyo Co., Ltd.) were placed in a 2000 ml four-necked flask. 0.366 mol), 109.32 g (0.839 mol) of potassium carbonate, and 548.71 g of N-ethyl-2-pyrrolidone were added, heated to 100° C., and stirred for 42 hours. After the temperature was lowered to 30° C. or lower, 382.80 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 3241.81 g of methanol and 648.36 g of pure water to precipitate a polymer. The resulting precipitate was filtered off, washed twice with 259.35 g of methanol, and dried under vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 13,968 and the yield was 71.91%. This polymer has a repeating unit structure represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000044
［式（３）において、ｎは１以上の数であり、１０≦ｎ≦５００である。］
Figure JPOXMLDOC01-appb-C000044
[In Formula (3), n is a number of 1 or more, and 10≦n≦500. ]
＜合成例２＞（ポリマー（４）の合成）
　１０００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン２５．００ｇ（０．１６５ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）２７．６３ｇ（０．０８６ｍｏｌ）、１，３－ビス［２－（４－ヒドロキシフェニル）－２－プロピル］ベンゼン３０．２８ｇ（０．０８６ｍｏｌ）、炭酸カリウム５４．６６ｇ（０．４２０ｍｏｌ）、Ｎ－エチル－２－ピロリドン１９４．１０ｇを入れて１００℃に昇温し、１００℃で４６時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン２７５．４３ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き、反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール８１９．８３ｇと純水１１６８．００ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１３０．６０ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は１１，７７８であり、収率は８８．６２％であった。このポリマーは、下記式（４）で表される繰り返し単位構造を有する。 <Synthesis Example 2> (Synthesis of Polymer (4))
25.00 g (0.165 mol) of 4,6-dichloropyrimidine and 27.63 g (Konishi Chemical Industry Co., Ltd.) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.) were placed in a 1000 ml four-necked flask. 0.086 mol), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene 30.28 g (0.086 mol), potassium carbonate 54.66 g (0.420 mol), N-ethyl-2 -Pyrrolidone 194.10 g was added, the temperature was raised to 100°C, and the mixture was stirred at 100°C for 46 hours. After the temperature was lowered to 30° C. or lower, 275.43 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 819.83 g of methanol and 1168.00 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 130.60 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 11,778 and the yield was 88.62%. This polymer has a repeating unit structure represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
＜合成例３＞（ポリマー（５）の合成）
　１０００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン２０．００ｇ（０．１３２ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）２２．３４ｇ（０．０６９ｍｏｌ）、スピロビクロマン２３．８１ｇ（０．０６９ｍｏｌ）、炭酸カリウム４３．７３ｇ（０．３３６ｍｏｌ）、Ｎ－エチル－２－ピロリドン１５４．７３ｇを入れて１００℃に昇温し４４時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン２１９．８６ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き、反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール６６７．２２ｇと純水９１１．７５ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１０４．２０ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は１４，３１３であり、収率は６８．００％であった。このポリマーは、下記式（５）で表される繰り返し単位構造を有する。 <Synthesis Example 3> (Synthesis of polymer (5))
20.00 g (0.132 mol) of 4,6-dichloropyrimidine and 22.34 g (Konishi Chemical Industry Co., Ltd.) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.) were placed in a 1000 ml four-necked flask. 0.069 mol), 23.81 g (0.069 mol) of spirobichroman, 43.73 g (0.336 mol) of potassium carbonate, and 154.73 g of N-ethyl-2-pyrrolidone are added, heated to 100° C. and stirred for 44 hours. bottom. After the temperature was lowered to 30° C. or lower, 219.86 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The obtained reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 667.22 g of methanol and 911.75 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 104.20 g of methanol, and dried under vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 14,313 and the yield was 68.00%. This polymer has a repeating unit structure represented by the following formula (5).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
＜合成例４＞（ポリマー（６）の合成）
　１００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン３．００ｇ（０．０２０ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）３．４２ｇ（０．０１１ｍｏｌ）、報告例（Ｐｏｌｙｍ．Ｃｈｅｍ．２０１２，３，２８９２）と同様に合成した４，４’－（ブタン－１，４－ジイルビス（オキシ））ジフェノール３．００ｇ（０．０１１ｍｏｌ）、炭酸カリウム６．５６ｇ（０．０５０ｍｏｌ）、Ｎ－エチル－２－ピロリドン２１．７１ｇを入れて１００℃に昇温し４９時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン２８．１５ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き、反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール１４６．４６ｇと純水２０８．１１ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１１．８２ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は２７，７３５であり、収率は８０．０１％であった。このポリマーは、下記式（６）で表される繰り返し単位構造を有する。 <Synthesis Example 4> (Synthesis of polymer (6))
3.00 g (0.020 mol) of 4,6-dichloropyrimidine and 3.42 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Kagaku Kogyo Co., Ltd.) were placed in a 100 ml four-necked flask. 0.011 mol), 3.00 g (0.011 mol) of 4,4′-(butane-1,4-diylbis(oxy))diphenol synthesized in the same manner as in the reported example (Polym.Chem.2012, 3, 2892) , 6.56 g (0.050 mol) of potassium carbonate, and 21.71 g of N-ethyl-2-pyrrolidone were added, heated to 100° C., and stirred for 49 hours. After the temperature was lowered to 30° C. or lower, 28.15 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 146.46 g of methanol and 208.11 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 11.82 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 27,735 and the yield was 80.01%. This polymer has a repeating unit structure represented by the following formula (6).
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
＜合成例５＞（ポリマー（７）の合成）
　１００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン３．００ｇ（０．０２０ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）３．３２ｇ（０．０１０ｍｏｌ）、報告例（Ｐｏｌｙｍ．Ｃｈｅｍ．２０１２，３，２８９２）と同様に合成した４，４’－（ヘキサン－１，６－ジイルビス（オキシ））ジフェノール３．２０ｇ（０．０１０ｍｏｌ）、炭酸カリウム６．５６ｇ（０．０５０ｍｏｌ）、Ｎ－エチル－２－ピロリドン２２．００ｇを入れて１００℃に昇温し４９時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン８９．００ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール１５１．１４ｇと純水２１６．３６ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１１．９２ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は１６，０１６であり、収率は７１．３４％であった。このポリマーは、下記式（７）で表される繰り返し単位構造を有する。 <Synthesis Example 5> (Synthesis of polymer (7))
3.00 g (0.020 mol) of 4,6-dichloropyrimidine and 3.32 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Kagaku Kogyo Co., Ltd.) were placed in a 100 ml four-necked flask. 0.010 mol), and 3.20 g (0.010 mol) of 4,4′-(hexane-1,6-diylbis(oxy))diphenol synthesized in the same manner as in the reported example (Polym.Chem.2012, 3, 2892) , 6.56 g (0.050 mol) of potassium carbonate, and 22.00 g of N-ethyl-2-pyrrolidone were added, heated to 100° C., and stirred for 49 hours. After the temperature was lowered to 30° C. or lower, 89.00 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 151.14 g of methanol and 216.36 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 11.92 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 16,016 and the yield was 71.34%. This polymer has a repeating unit structure represented by the following formula (7).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
＜合成例６＞（ポリマー（８）の合成）
　１００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン３．００ｇ（０．０２０ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）３．３５ｇ（０．０１０ｍｏｌ）、報告例（Ｐｏｌｙｍ．Ｃｈｅｍ．２０１２，３，２８９２）と同様に合成した４，４’－（オクタン－１，８－ジイルビス（オキシ））ジフェノール３．５４ｇ（０．０１０ｍｏｌ）、炭酸カリウム６．５６ｇ（０．０５０ｍｏｌ）、Ｎ－エチル－２－ピロリドン２３．１１ｇを入れて１００℃に昇温し３０時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン８９．００ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール１５６．１７ｇと純水２１５．３１ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１２．２９ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は２８，６０７であり、収率は７０．５７％であった。このポリマーは、下記式（８）で表される繰り返し単位構造を有する。 <Synthesis Example 6> (Synthesis of Polymer (8))
3.00 g (0.020 mol) of 4,6-dichloropyrimidine and 3.35 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.) were placed in a 100-ml four-neck flask ( 0.010 mol), 3.54 g (0.010 mol) of 4,4′-(octane-1,8-diylbis(oxy))diphenol synthesized in the same manner as in the reported example (Polym.Chem.2012, 3, 2892) , 6.56 g (0.050 mol) of potassium carbonate, and 23.11 g of N-ethyl-2-pyrrolidone were added, heated to 100° C., and stirred for 30 hours. After the temperature was lowered to 30° C. or lower, 89.00 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The obtained reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 156.17 g of methanol and 215.31 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 12.29 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 28,607 and the yield was 70.57%. This polymer has a repeating unit structure represented by the following formula (8).
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
＜合成例７＞（ポリマー（９）の合成）
　２００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン６．００ｇ（０．０３３ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）６．７０ｇ（０．０２１ｍｏｌ）、９，９－ビス（４－ヒドロキシフェニル）フルオレン（東京化成工業（株））７．３５ｇ（０．０２１ｍｏｌ）、炭酸カリウム１３．１２ｇ（０．１００ｍｏｌ）、Ｎ－エチル－２－ピロリドン４７．０５ｇを入れて１００℃に昇温し２６時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン６６．５１ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール２１６．６ｇと純水２１６．６ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール３１．５４ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は２４，１５３であり、収率は９７．９１％であった。このポリマーは、下記式（９）で表される繰り返し単位構造を有する。 <Synthesis Example 7> (Synthesis of Polymer (9))
6.00 g (0.033 mol) of 4,6-dichloropyrimidine and 6.70 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.) were placed in a 200-ml four-necked flask ( 0.021 mol), 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.) 7.35 g (0.021 mol), potassium carbonate 13.12 g (0.100 mol), N-ethyl-2 -Pyrrolidone 47.05 g was added, the temperature was raised to 100°C, and the mixture was stirred for 26 hours. After the temperature was lowered to 30° C. or lower, 66.51 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 216.6 g of methanol and 216.6 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 31.54 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 24,153 and the yield was 97.91%. This polymer has a repeating unit structure represented by the following formula (9).
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
＜合成例８＞（ポリマー（１０）の合成）
　２００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン３．００ｇ（０．０２０ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）３．３０ｇ（０．０１０ｍｏｌ）、報告例（特開平４－３６８３５０）と同様に合成した４，４’－（１，３－フェニレンビス（プロパン－２，２－ジイル））ビス（２－アリルフェノール）４．４３ｇ（０．０１０ｍｏｌ）、炭酸カリウム６．５６ｇ（０．０５０ｍｏｌ）、Ｎ－エチル－２－ピロリドン２５．６３ｇを入れて１００℃に昇温し３７時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン３５．１３ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール１０９．２ｇと純水１０７．３ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１６．７ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は２２，４９０であり、収率は８３．９０％であった。このポリマーは、下記式（１０）で表される繰り返し単位構造を有する。 <Synthesis Example 8> (Synthesis of Polymer (10))
3.00 g (0.020 mol) of 4,6-dichloropyrimidine and 3.30 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.) were placed in a 200-ml four-necked flask ( 0.010 mol); 43 g (0.010 mol), 6.56 g (0.050 mol) of potassium carbonate, and 25.63 g of N-ethyl-2-pyrrolidone were added, heated to 100° C., and stirred for 37 hours. After the temperature was lowered to 30° C. or lower, 35.13 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 109.2 g of methanol and 107.3 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 16.7 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,490 and the yield was 83.90%. This polymer has a repeating unit structure represented by the following formula (10).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
＜合成例９＞（ポリマー（１１）の合成）
　２００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン３．００ｇ（０．０２０ｍｏｌ）、報告例（特開平４－３６８３５０）と同様に合成した４，４’－（１，３－フェニレンビス（プロパン－２，２－ジイル））ビス（２－アリルフェノール）８．８６ｇ（０．０２１ｍｏｌ）、炭酸カリウム６．５６ｇ（０．０５０ｍｏｌ）、Ｎ－エチル－２－ピロリドン２１．１１ｇを入れて１００℃に昇温し３７時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン４６．０５ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール１１６．２ｇと純水１１６．３ｇに滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール１８．２ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は３７，２６２であり、収率は８７．０１％であった。このポリマーは、下記式（１１）で表される繰り返し単位構造を有する。 <Synthesis Example 9> (Synthesis of Polymer (11))
3.00 g (0.020 mol) of 4,6-dichloropyrimidine and 4,4'-(1,3-phenylenebis( Propane-2,2-diyl))bis(2-allylphenol) 8.86 g (0.021 mol), potassium carbonate 6.56 g (0.050 mol), N-ethyl-2-pyrrolidone 21.11 g, and 100 ℃ and stirred for 37 hours. After the temperature was lowered to 30° C. or lower, 46.05 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to 116.2 g of methanol and 116.3 g of pure water to precipitate a polymer. The obtained precipitate was separated by filtration, washed twice with 18.2 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 37,262 and the yield was 87.01%. This polymer has a repeating unit structure represented by the following formula (11).
Figure JPOXMLDOC01-appb-C000052
［式（１１）において、ｎは１以上の数であり、１０≦ｎ≦５００である。］
Figure JPOXMLDOC01-appb-C000052
[In Formula (11), n is a number of 1 or more, and 10≦n≦500. ]
＜合成例１０＞（ポリマー（１２）の合成）
　３００ミリリットル容量の四口フラスコに４，６－ジクロロピリミジン１５．００ｇ（０．０９８ｍｏｌ）、２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン（小西化学工業株式会社）１６．３３ｇ（０．０５１ｍｏｌ）、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン（東京化成工業（株））１３．９２ｇ（０．０５１ｍｏｌ）、炭酸カリウム３９．３５ｇ（０．３０２ｍｏｌ）、Ｎ－エチル－２－ピロリドン１０３．０２ｇを入れて１００℃に昇温し２０時間攪拌した。３０℃以下に降温した後、テトラヒドロフラン１５３．２７ｇを入れて希釈し、反応液に生じた沈殿物をろ過により取り除き反応混合物を得た。得られた反応混合物を６Ｎ塩酸／Ｎ－エチル－２－ピロリドン（１：９）溶液でｐＨ４に調整した後、メタノール４５２．１ｇと純水４５２．１ｇの混合溶媒に滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、ろ物をメタノール７２．３ｇで二回洗浄し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は４３，１１６であり、収率は７３％であった。このポリマーは、下記式（１２）で表される繰り返し単位構造を有する。 <Synthesis Example 10> (Synthesis of polymer (12))
15.00 g (0.098 mol) of 4,6-dichloropyrimidine and 16.33 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Kagaku Kogyo Co., Ltd.) were placed in a 300 ml four-necked flask. 0.051 mol), 1,1-bis(4-hydroxyphenyl)cyclohexane (Tokyo Chemical Industry Co., Ltd.) 13.92 g (0.051 mol), potassium carbonate 39.35 g (0.302 mol), N-ethyl-2 -Pyrrolidone 103.02 g was added, the temperature was raised to 100°C, and the mixture was stirred for 20 hours. After the temperature was lowered to 30° C. or lower, 153.27 g of tetrahydrofuran was added for dilution, and precipitates formed in the reaction solution were removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid/N-ethyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solvent of 452.1 g of methanol and 452.1 g of pure water to precipitate the polymer. rice field. The obtained precipitate was separated by filtration, washed twice with 72.3 g of methanol, and dried in a vacuum to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 43,116 and the yield was 73%. This polymer has a repeating unit structure represented by the following formula (12).
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
＜実施例１＞
　合成例１で得られたポリマー（３）６．３２ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）６．３２ｇをシクロヘキサノン１８．９６ｇに溶解させ、組成物を調製した。その後、孔径５μｍのポリテトラフルオロエチレン（以下、本明細書ではＰＴＦＥと略称する。）製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 1>
18.96 g of cyclohexanone was added to 6.32 g of polymer (3) obtained in Synthesis Example 1, 6.32 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Thereafter, the mixture was filtered using a polytetrafluoroethylene (hereinafter abbreviated as PTFE in this specification) microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例２＞
　合成例２で得られたポリマー（４）１５．８０ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）１５．８０ｇをシクロヘキサノン４７．３９ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 2>
15.80 g of the polymer (4) obtained in Synthesis Example 2, 15.80 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 47.39 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例３＞
　合成例３で得られたポリマー（５）６．３２ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）６．３２ｇをシクロヘキサノン１８．９６ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 3>
18.96 g of cyclohexanone was added to 6.32 g of the polymer (5) obtained in Synthesis Example 3 and 6.32 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例４＞
　合成例４で得られたポリマー（６）２．５３ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）２．５３ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 4>
2.53 g of the polymer (6) obtained in Synthesis Example 4, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例５＞
　合成例５で得られたポリマー（７）２．５３ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）２．５３ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 5>
2.53 g of the polymer (7) obtained in Synthesis Example 5, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例６＞
　合成例６で得られたポリマー（８）２．５３ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）２．５３ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 6>
2.53 g of the polymer (8) obtained in Synthesis Example 6, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例７＞
　合成例７で得られたポリマー（９）２．５３ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）２．５３ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 7>
2.53 g of the polymer (9) obtained in Synthesis Example 7, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例８＞
　合成例８で得られたポリマー（１０）４．２１ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）０．８４ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 8>
4.21 g of the polymer (10) obtained in Synthesis Example 8, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例９＞
　合成例９で得られたポリマー（１１）４．２１ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）０．８４ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 9>
7.58 g of cyclohexanone was added to 4.21 g of polymer (11) obtained in Synthesis Example 9, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１０＞
　合成例１０で得られたポリマー（１２）４．２５ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）０．８５ｇをシクロヘキサノン９．４８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 10>
9.48 g of cyclohexanone was added to 4.25 g of the polymer (12) obtained in Synthesis Example 10 and 0.85 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I. Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１１＞
　合成例１で得られたポリマー（３）４．７４ｇをシクロヘキサノン７．１１ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 11>
A composition was prepared by dissolving 4.74 g of the polymer (3) obtained in Synthesis Example 1 in 7.11 g of cyclohexanone. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１２＞
　合成例２で得られたポリマー（４）７．５８ｇをシクロヘキサノン１５．１６ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 12>
A composition was prepared by dissolving 7.58 g of polymer (4) obtained in Synthesis Example 2 in 15.16 g of cyclohexanone. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１３＞
　合成例１で得られたポリマー（３）４．２１ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）０．８４ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 13>
4.21 g of the polymer (3) obtained in Synthesis Example 1, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.) was added to 7.58 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１４＞
　合成例２で得られたポリマー（４）４．２１ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）０．８４ｇをシクロヘキサノン７．５８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 14>
7.58 g of cyclohexanone was added to 4.21 g of the polymer (4) obtained in Synthesis Example 2, 0.84 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１５＞
　合成例２で得られたポリマー（４）５．０５ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）１．２６ｇをシクロヘキサノン９．４８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 15>
9.48 g of cyclohexanone was added to 5.05 g of the polymer (4) obtained in Synthesis Example 2 and 1.26 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１６＞
　合成例２で得られたポリマー（４）３．７９ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）２．５３ｇをシクロヘキサノン９．４８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 16>
3.79 g of the polymer (4) obtained in Synthesis Example 2, 2.53 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I Kasei Co., Ltd.) was added to 9.48 g of cyclohexanone. to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜実施例１７＞
　合成例２で得られたポリマー（４）２．５３ｇ、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン（ケイ・アイ化成株式会社製）３．７９ｇをシクロヘキサノン９．４８ｇに溶解させ、組成物を調製した。その後、孔径５μｍのＰＴＦＥ製マイクロフィルターを用いてろ過して、非感光性樹脂組成物を調製した。 <Example 17>
9.48 g of cyclohexanone was added to 2.53 g of the polymer (4) obtained in Synthesis Example 2 and 3.79 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K-I Kasei Co., Ltd.). to prepare a composition. Then, it was filtered using a PTFE microfilter with a pore size of 5 μm to prepare a non-photosensitive resin composition.
＜比較例１＞
　テトラヒドロフラン１０．００ｇに２，２－ビス（４－シアナトフェニル）プロパン９．００ｇと４，４’－ビスマレイミドフェニルメタン１．００ｇを溶解して、さらに硬化触媒のアセチルアセトン鉄０．１０ｇを溶解して溶液を調製した。調製した溶液を、シリコンウェハに積層させたアルミ箔上にスピンコーターを用いて塗布し、７５℃、５分プリベークし、更に真空下で１００℃、１時間、さらに１６０℃４時間ベークして厚さ１０－３０μｍ程度のＢＴレジン膜を形成した。 <Comparative Example 1>
Dissolve 9.00 g of 2,2-bis(4-cyanatophenyl)propane and 1.00 g of 4,4'-bismaleimidophenylmethane in 10.00 g of tetrahydrofuran, and further dissolve 0.10 g of iron acetylacetone as a curing catalyst. to prepare a solution. The prepared solution was applied using a spin coater onto an aluminum foil laminated on a silicon wafer, prebaked at 75°C for 5 minutes, and further baked at 100°C for 1 hour and then at 160°C for 4 hours under vacuum to obtain a thick layer. A BT resin film having a thickness of about 10 to 30 μm was formed.
　［電気特性試験］
　実施例１～１７で調製した非感光性樹脂組成物を、シリコンウェハに積層させたアルミ箔上にスピンコーターを用いて塗布し、１００℃、５分プリベークし、さらに窒素下で２３０℃、４時間ベークし、膜厚１０－２０μｍ程度の膜を形成した。その後６Ｎ塩酸中に浸漬させた。アルミが溶解し、膜が浮き上がったところを回収し、縦７．５ｃｍ、横６．３ｃｍにカットし自立膜を得た。この自立膜を用いてスプリットシリンダー式空洞共振法にて、自立膜取得直後の、１０ＧＨｚにおける比誘電率及び誘電正接を算出した。比較例１についても同様に塩酸処理・カッティングを行い、スプリットシリンダー式空洞共振法にて測定を行った。測定方法の詳細は以下の通りである。
（測定方法）
スプリットシリンダー式空洞共振法
（装置構成）
ベクトルネットワークアナライザ：　Ｎ５２２７Ａ ＰＮＡネットワークアナライザー（キーサイト・テクノロジーズ・インク製）
共振器：　ＣＲ－７１０（ＥＭラボ株式会社製）
測定周波数：約１０ＧＨｚ（サンプルの共振周波数に依存） [Electrical property test]
The non-photosensitive resin composition prepared in Examples 1 to 17 was applied using a spin coater onto an aluminum foil laminated on a silicon wafer, prebaked at 100 ° C. for 5 minutes, and further baked at 230 ° C. for 4 minutes under nitrogen. It was baked for a period of time to form a film having a thickness of about 10-20 μm. After that, it was immersed in 6N hydrochloric acid. Aluminum was dissolved, and the part where the film floated was recovered and cut into a length of 7.5 cm and a width of 6.3 cm to obtain a self-supporting film. Using this self-supporting film, the dielectric constant and dielectric loss tangent at 10 GHz immediately after obtaining the self-supporting film were calculated by the split-cylinder cavity resonance method. Comparative Example 1 was similarly treated with hydrochloric acid and cut, and measured by the split-cylinder cavity resonance method. The details of the measurement method are as follows.
(Measuring method)
Split-cylinder cavity resonance method (equipment configuration)
Vector network analyzer: N5227A PNA network analyzer (manufactured by Keysight Technologies Inc.)
Resonator: CR-710 (manufactured by EM Lab Co., Ltd.)
Measurement frequency: about 10 GHz (depending on sample resonance frequency)
測定結果を以下の表１に示す。 The measurement results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000054
　本発明に係る非感光性絶縁膜形成組成物によれば、ＢＴレジンに対して低比誘電率及び低誘電正接を示す硬化膜が提供される。 According to the composition for forming a non-photosensitive insulating film according to the present invention, a cured film exhibiting a low dielectric constant and a low dielectric loss tangent to BT resin is provided.

Claims (16)

  1. 　下記式（１）：
    Figure JPOXMLDOC01-appb-C000001
    ［式（１）において、
    基Ａ１は、
    Figure JPOXMLDOC01-appb-C000002
    で表される５乃至８員芳香族複素環を表し、
    当該芳香族複素環は架橋性置換基を有してもよく、
    基Ａ２は、
    Figure JPOXMLDOC01-appb-C000003
    で表される５乃至８員芳香族複素環を表し、
    当該芳香族複素環は架橋性置換基を有してもよく、
    基Ｂ１は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有する炭素原子数６乃至４０の有機基を表し、
    基Ｂ２は、Ｎ、Ｓ及びＯから選択される少なくとも１つのヘテロ原子を含んでもよく、ハロゲン原子を含んでもよい、架橋性置換基を有さない炭素原子数６乃至４０の有機基を表し、
    ｎ１、ｎ２はそれぞれ独立に０以上、１以下の数であり、
    ｍ１、ｍ２はそれぞれ独立に０以上、１以下の数であり、
    ｎは１以上の数であり、
    ｍは０以上の数であり、
    １０≦ｎ＋ｍ≦５００であり、
    但し、基Ａ１、基Ａ２が共に架橋性置換基を有しないとき、
    ｍ≠０であればｎ１及びｍ１の少なくとも一方は１であり、
    ｍ＝０であればｎ１は１である。］
    で表される繰り返し単位構造を有するポリマー、及び
    　溶媒
    　を含む非感光性絶縁膜形成組成物。     Formula (1) below:
    Figure JPOXMLDOC01-appb-C000001
    [In formula (1),
    Group A 1 is
    Figure JPOXMLDOC01-appb-C000002
    represents a 5- to 8-membered aromatic heterocycle represented by
    The aromatic heterocycle may have a crosslinkable substituent,
    Group A2 is
    Figure JPOXMLDOC01-appb-C000003
    represents a 5- to 8-membered aromatic heterocycle represented by
    The aromatic heterocycle may have a crosslinkable substituent,
    Group B 1 represents an organic group having 6 to 40 carbon atoms and having a crosslinkable substituent which may contain at least one heteroatom selected from N, S and O and may contain a halogen atom,
    Group B2 represents an organic group having 6 to 40 carbon atoms and having no bridging substituents and optionally containing at least one heteroatom selected from N, S and O and optionally containing a halogen atom. ,
    n 1 and n 2 are each independently a number of 0 or more and 1 or less,
    m 1 and m 2 are each independently a number of 0 or more and 1 or less,
    n is a number of 1 or more,
    m is a number of 0 or more,
    10≦n+m≦500,
    However, when both the group A 1 and the group A 2 do not have a crosslinkable substituent,
    at least one of n1 and m1 is 1 if m≠0;
    n1 is 1 if m=0. ]
    A non-photosensitive insulating film-forming composition comprising a polymer having a repeating unit structure represented by and a solvent.
  2. 架橋剤をさらに含む、請求項１に記載の非感光性絶縁膜形成組成物。 The non-photosensitive insulating film-forming composition according to claim 1, further comprising a cross-linking agent.
  3. 前記架橋剤がビスマレイミド化合物である、請求項２に記載の非感光性絶縁膜形成組成物。 3. The composition for forming a non-photosensitive insulating film according to claim 2, wherein said cross-linking agent is a bismaleimide compound.
  4. 　基Ａ１が、
    Figure JPOXMLDOC01-appb-C000004
    で表される芳香族複素環を表し、当該芳香族複素環は架橋性置換基を有してもよい、
    請求項１乃至３のいずれか一項に記載の非感光性絶縁膜形成組成物。     Group A 1 is
    Figure JPOXMLDOC01-appb-C000004
    Represents an aromatic heterocycle represented by the aromatic heterocycle may have a crosslinkable substituent,
    The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 3.
  5. 　基Ａ２が、
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
    及び
    Figure JPOXMLDOC01-appb-C000007
    で表される芳香族複素環からなる群より選択される少なくとも一種の芳香族複素環を表し、これらの芳香族複素環はいずれも架橋性置換基を有してもよい、
    請求項１乃至４のいずれか一項に記載の非感光性絶縁膜形成組成物。     Group A2 is
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
    as well as
    Figure JPOXMLDOC01-appb-C000007
    Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by any of these aromatic heterocycles may have a crosslinkable substituent,
    The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 4.
  6. 　基Ｂ１が、下記から選択される少なくとも１種である、
    Figure JPOXMLDOC01-appb-C000008
    （式中、Ｇは直接結合、又は下記式のいずれかを表す。
    Figure JPOXMLDOC01-appb-C000009
    Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。）
    請求項１乃至５のいずれか一項に記載の非感光性絶縁膜形成組成物。     Group B 1 is at least one selected from
    Figure JPOXMLDOC01-appb-C000008
    (In the formula, G represents either a direct bond or the following formula.
    Figure JPOXMLDOC01-appb-C000009
    L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
    The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 5.
  7. 　基Ｂ１が、
    Figure JPOXMLDOC01-appb-C000010
    で表される
    請求項１乃至６のいずれか一項に記載の非感光性絶縁膜形成組成物。     Group B 1 is
    Figure JPOXMLDOC01-appb-C000010
    The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 6, represented by.
  8. 　基Ｂ２が、下記から選択される少なくとも１種である、
    Figure JPOXMLDOC01-appb-C000011
    （式中、Ｇは直接結合、又は下記式のいずれかを表す。
    Figure JPOXMLDOC01-appb-C000012
    Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。）
    請求項１乃至７のいずれか一項に記載の非感光性絶縁膜形成組成物。     Group B2 is at least one selected from
    Figure JPOXMLDOC01-appb-C000011
    (In the formula, G represents either a direct bond or the following formula.
    Figure JPOXMLDOC01-appb-C000012
    L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
    The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 7.
  9. 　基Ｂ２が、下記から選択される少なくとも１種である、
    Figure JPOXMLDOC01-appb-C000013
    （式中、Ｇ１及びＧ２はそれぞれ独立に、直接結合、又は下記式のいずれかを表す。
    Figure JPOXMLDOC01-appb-C000014
    Ｌ、Ｍはそれぞれ独立に水素原子、フェニル基、又は炭素原子数１～３のアルキル基を表す。）
    請求項１乃至７のいずれか一項に記載の非感光性絶縁膜形成組成物。     Group B2 is at least one selected from
    Figure JPOXMLDOC01-appb-C000013
    (In the formula, G1 and G2 each independently represent either a direct bond or the following formula.
    Figure JPOXMLDOC01-appb-C000014
    L and M each independently represent a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. )
    The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 7.
  10. 　架橋性置換基がラジカル架橋性基を含む、請求項１乃至９のいずれか一項に記載の非感光性絶縁膜形成組成物。 The non-photosensitive insulating film-forming composition according to any one of claims 1 to 9, wherein the crosslinkable substituent contains a radical crosslinkable group.
  11. 　架橋性置換基が、（メタ）アクリレート基、マレイミド基、又はアリル基を含む、請求項１乃至１０のいずれか一項に記載の非感光性絶縁膜形成組成物。 The non-photosensitive insulating film-forming composition according to any one of claims 1 to 10, wherein the crosslinkable substituent contains a (meth)acrylate group, a maleimide group, or an allyl group.
  12. 　ｍ＝０である、請求項１乃至１１のいずれか一項に記載の非感光性絶縁膜形成組成物。 The non-photosensitive insulating film-forming composition according to any one of claims 1 to 11, wherein m = 0.
  13. 　前記溶媒の沸点が、２３０℃以下である、請求項１乃至１２のいずれか一項に記載の非感光性絶縁膜形成組成物。 The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 12, wherein the solvent has a boiling point of 230°C or lower.
  14. 前記溶媒の沸点が２００℃以下である、請求項１乃至１３のいずれか一項に記載の非感光性絶縁膜形成組成物。 The composition for forming a non-photosensitive insulating film according to any one of claims 1 to 13, wherein the solvent has a boiling point of 200°C or lower.
  15. 　請求項１乃至１４の何れか１項に記載の非感光性絶縁膜形成組成物の塗布膜の硬化物であることを特徴とする非感光性樹脂膜。 A non-photosensitive resin film characterized by being a cured product of a coating film of the composition for forming a non-photosensitive insulating film according to any one of claims 1 to 14.
  16. 　誘電正接が０．０１未満である、請求項１５に記載の非感光性樹脂膜。 The non-photosensitive resin film according to claim 15, which has a dielectric loss tangent of less than 0.01.
PCT/JP2022/032691 2021-09-21 2022-08-31 Non-photosensitive insulation film-forming composition WO2023047901A1 (en)

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