WO2023047901A1 - Composition filmogène d'isolation non photosensible - Google Patents

Composition filmogène d'isolation non photosensible 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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English (en)
Japanese (ja)
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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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    • 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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  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

La présente invention concerne : une composition filmogène d'isolation non photosensible permettant d'obtenir une faible constante diélectrique et une faible tangente de perte diélectrique ; et un film de résine non photosensible obtenu à partir de ladite composition.　Cette composition filmogène d'isolation non photosensible contient un solvant et un polymère qui a une structure d'unité de répétition représentée par la formule (1). (Dans la formule (1), le groupe A1 représente un hétérocycle aromatique représenté par (AA) ; le groupe A2 représente un hétérocycle aromatique représenté par (BB) ; le groupe A1 et le groupe A2 peuvent avoir des substituants réticulables ; le groupe B1 représente un groupe organique ayant un substituant réticulable ; et le groupe B2 représente un groupe organique n'ayant pas de substituant réticulable).
PCT/JP2022/032691 2021-09-21 2022-08-31 Composition filmogène d'isolation non photosensible WO2023047901A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110108755A1 (en) * 2009-11-12 2011-05-12 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Heteroaromatic phthalonitriles
JP2017200997A (ja) * 2016-04-27 2017-11-09 Jsr株式会社 組成物、硬化物及び積層体
JP2019051709A (ja) * 2017-09-15 2019-04-04 Jsr株式会社 高周波回路用積層体及びその製造方法、並びにｂステージシート
WO2019198606A1 (fr) * 2018-04-09 2019-10-17 日本化薬株式会社 Composé contenant un groupe alcényle, composition de résine durcissable, et objet durci obtenu à partir de cette dernière
CN112457651A (zh) * 2020-11-30 2021-03-09 南亚新材料科技股份有限公司 生物基树脂组合物、粘结片、覆金属箔层压板及印刷线路板
WO2021187481A1 (fr) * 2020-03-18 2021-09-23 日産化学株式会社 Composition filmogène isolante photosensible
JP2021172756A (ja) * 2020-04-27 2021-11-01 味の素株式会社 樹脂組成物
WO2022210095A1 (fr) * 2021-04-02 2022-10-06 Jsr株式会社 Polymère, composition, produit durci, corps multicouche et composant électronique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110108755A1 (en) * 2009-11-12 2011-05-12 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Heteroaromatic phthalonitriles
JP2017200997A (ja) * 2016-04-27 2017-11-09 Jsr株式会社 組成物、硬化物及び積層体
JP2019051709A (ja) * 2017-09-15 2019-04-04 Jsr株式会社 高周波回路用積層体及びその製造方法、並びにｂステージシート
WO2019198606A1 (fr) * 2018-04-09 2019-10-17 日本化薬株式会社 Composé contenant un groupe alcényle, composition de résine durcissable, et objet durci obtenu à partir de cette dernière
WO2021187481A1 (fr) * 2020-03-18 2021-09-23 日産化学株式会社 Composition filmogène isolante photosensible
JP2021172756A (ja) * 2020-04-27 2021-11-01 味の素株式会社 樹脂組成物
CN112457651A (zh) * 2020-11-30 2021-03-09 南亚新材料科技股份有限公司 生物基树脂组合物、粘结片、覆金属箔层压板及印刷线路板
WO2022210095A1 (fr) * 2021-04-02 2022-10-06 Jsr株式会社 Polymère, composition, produit durci, corps multicouche et composant électronique

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