Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/22—Polybenzoxazoles
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0346—Organic insulating material consisting of one material containing N

Definitions

• the present disclosure relates to fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles.
• Polybenzoxazole resin like polyimide resin, is a resin with excellent heat resistance and mechanical properties. is used as For application to such electrical and electronic materials, methods for producing polyhydroxyamide, which is a highly pure polybenzoxazole precursor containing no ionic impurities, have been proposed (Patent Documents 1 and 2).
• R 1 is a divalent aromatic residue containing one or more elements selected from O, N, S, F and Si in its structure, or a 2 having 1 to 12 carbon atoms.
• R 2 represents an alkyl group having 1 to 4 carbon atoms or an aromatic residue having 6 to 8 carbon atoms.
• a polybenzoxazole precursor resin obtained by the polymerization reaction of (1) having a weight average molecular weight in the range of 10,000 to 1,000,000 and an ionic impurity content of 10 ppm or less. Precursor resins are described.
• JP-A-9-183846 JP 2011-256219 A JP-A-2000-212281 JP-A-2000-219742 JP-A-2006-45321
• An object of the present disclosure is to provide a highly soluble fluorine-containing polyamide compound capable of obtaining a fluorine-containing polybenzoxazole having a low dielectric constant and a low dielectric loss tangent to the extent that it can be applied to a high-frequency printed circuit board.
• Another object of the present disclosure is to provide a fluorine-containing polybenzoxazole that has a low dielectric constant and a low dielectric loss tangent to the extent that it can be applied to high-frequency printed circuit boards.
• a fluorine-containing polyamide compound having a repeating unit represented by formula (1) is provided.
• Formula (1) (In formula (1), n is an integer of 1 to 8, L is a linking group, and ring A and ring B independently represent a hydrocarbon ring.)
• ring A is preferably a cyclohexane ring, benzene ring, naphthalene ring, biphenyl ring, anthracene ring or terphenyl ring.
• ring B is preferably a cyclohexane ring, benzene ring, naphthalene ring, biphenyl ring, anthracene ring or terphenyl ring.
• the linking group is preferably a single bond, —SO 2 —, —O—, —CO—, a divalent non-fluorinated organic group or a divalent fluorinated organic group.
• the repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-1).
• Formula (1-1) (In formula (1-1), n and L are as described above.)
• the average degree of polymerization of the repeating unit represented by formula (1) is preferably 2-100.
• the present disclosure also provides a fluorine-containing polybenzoxazole having a repeating unit represented by formula (2).
• Formula (2) (In formula (2), n is an integer of 1 to 8, L is a linking group, and ring A and ring B independently represent a hydrocarbon ring.)
• ring A is preferably a cyclohexane ring, benzene ring, naphthalene ring, biphenyl ring, anthracene ring or terphenyl ring.
• ring B is preferably a cyclohexane ring, benzene ring, naphthalene ring, biphenyl ring, anthracene ring or terphenyl ring.
• the linking group is preferably a single bond, —SO 2 —, —O—, —CO—, a divalent non-fluorinated organic group or a divalent fluorinated organic group.
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-1).
• the average degree of polymerization of the repeating unit represented by formula (2) is preferably 2-100.
• a low dielectric material containing the fluorine-containing polyamide compound or the fluorine-containing polybenzoxazole is provided.
• an insulating material for printed circuit boards containing the fluorine-containing polyamide compound or the fluorine-containing polybenzoxazole.
• a highly soluble fluorine-containing polyamide compound that can provide a fluorine-containing polybenzoxazole having a low dielectric constant and a low dielectric loss tangent.
• a fluorine-containing polybenzoxazole having a low dielectric constant and a low dielectric loss tangent it is possible to provide a fluorine-containing polybenzoxazole having a low dielectric constant and a low dielectric loss tangent.
• the fluorine-containing polyamide compound of the present disclosure has a repeating unit represented by formula (1).
• n is an integer of 1 to 8
• L is a linking group
• ring A and ring B independently represent a hydrocarbon ring.
• n represents an integer from 1 to 8. n is preferably an integer of 4 to 8, more preferably 4, 6 or 8.
• L represents a linking group.
• the linking group is preferably a single bond, —SO 2 —, —O—, —CO—, a divalent non-fluorinated organic group or a divalent fluorinated organic group, and a single bond, —O—, or divalent
• a non-fluorinated organic group or a divalent fluorinated organic group is more preferred, a divalent non-fluorinated organic group or a divalent fluorinated organic group is more preferred, and a divalent fluorinated organic group is particularly preferred.
• the non-fluorinated organic group is a divalent organic group having no fluorine atom.
• a linear or branched non-fluorinated alkylene group or non-fluorinated arylene group is preferable.
• the fluorinated organic group is a divalent organic group having one or more fluorine atoms.
• L is preferably a linear or branched fluorinated alkylene group.
• a perfluoroalkylene group is preferable as the fluorinated alkylene group.
• the number of carbon atoms in the fluorinated alkylene group is preferably 1 to 15, more preferably 2 or more, because the dielectric constant and dielectric loss tangent of the fluorine-containing polyamide compound can be lowered and the solubility can be further increased. Yes, more preferably 10 or less, still more preferably 6 or less.
• fluorinated alkylene group -C(CF 3 ) 2 - is preferred.
• Ring A and ring B independently represent a hydrocarbon ring.
• the hydrocarbon ring may be monocyclic or polycyclic, and may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.
• An aliphatic hydrocarbon ring may be a saturated or unsaturated hydrocarbon ring having no aromatic character.
• the carbonyl group and difluoromethylene group adjacent to the hydrocarbon ring of ring A are not particularly limited in the position of bonding to the hydrocarbon ring, and may be bonded to any carbon atom among the carbon atoms constituting the hydrocarbon ring. can.
• the number of carbon atoms in ring A is preferably 3 to 30, more preferably 5 or more, still more preferably 6 or more, more preferably 20 or less, still more preferably 18 or less.
• the hydrocarbon ring of ring A may or may not have a substituent.
• substituents include halogen atoms such as a fluorine atom, alkyl groups such as a methyl group, halogenated alkyl groups such as a trifluoromethyl group, and aryl groups such as a phenyl group.
• monocyclic saturated hydrocarbon rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring; monocyclic non-aromatic unsaturated hydrocarbon rings such as cyclopropene ring, cyclobutene ring, cyclopropene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring; Polycyclic non-aromatic hydrocarbon rings such as norbornene ring, norbornadiene ring, decahydronaphthalene ring, bicycloundecane ring, and spirobicyclopentane ring; benzene ring, n
• ring A is preferably a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring or a terphenyl ring, more preferably a benzene ring. These may or may not have a substituent.
• the amino group adjacent to the hydrocarbon ring of ring B and the linking group of L are not particularly limited in the position of bonding to the hydrocarbon ring, and may be bonded to any carbon atom among the carbon atoms constituting the hydrocarbon ring. can be done.
• the number of carbon atoms in ring B is preferably 3 to 30, more preferably 5 or more, still more preferably 6 or more, more preferably 20 or less, still more preferably 18 or less.
• the hydrocarbon ring of ring B may or may not have a substituent.
• substituents include halogen atoms such as a fluorine atom, alkyl groups such as a methyl group, halogenated alkyl groups such as a trifluoromethyl group, and aryl groups such as a phenyl group.
• monocyclic saturated hydrocarbon rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring; monocyclic non-aromatic unsaturated hydrocarbon rings such as cyclopropene ring, cyclobutene ring, cyclopropene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring; Polycyclic non-aromatic hydrocarbon rings such as norbornene ring, norbornadiene ring, decahydronaphthalene ring, bicycloundecane ring, and spirobicyclopentane ring; benzene ring, n
• ring B is preferably a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring or a terphenyl ring, and more preferably a benzene ring. These may or may not have a substituent.
• the repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-1).
• the average degree of polymerization of the repeating unit represented by formula (1) is preferably 200 or less, more preferably 150 or less, still more preferably 100 or less, and 2 or more. and may be 3 or more.
• the average degree of polymerization is calculated from the number average molecular weight (Mn) of the fluorine-containing polyamide compound of the present disclosure.
• the number average molecular weight (Mn) of the fluorine-containing polyamide compound of the present disclosure is preferably 10,000 or more, more preferably 20,000 or more, and preferably 1,000,000 in terms of standard polystyrene by gel permeation chromatography (GPC). or less, more preferably 500,000 or less.
• the molecular weight distribution (Mw/Mn) of the fluorine-containing polyamide compound of the present disclosure is preferably 2 or more, preferably 5 or less, more preferably 4 or less in terms of standard polystyrene by gel permeation chromatography (GPC). be.
• the logarithmic viscosity ⁇ inh of the fluorine-containing polyamide compound of the present disclosure is preferably 0.3 dL/g or more, more preferably 0.5 dL/g or more.
• the logarithmic viscosity ⁇ inh is obtained by dissolving a fluorine-containing polyamide compound in a solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a solution with a solution concentration of 0.5 g / dL, and measuring the obtained solution at 30 ° C. can be calculated by the following formula.
• Logarithmic viscosity ⁇ inh ln (solution viscosity/solvent viscosity)/solution concentration
• the fluorine-containing polyamide compound of the present disclosure can be suitably used as a precursor of a fluorine-containing polybenzoxazole having a repeating unit represented by formula (2) described below.
• the fluorine-containing polybenzoxazole of the present disclosure has a repeating unit represented by formula (2).
• Formula (2) (In formula (2), n is an integer of 1 to 8, L is a linking group, and ring A and ring B independently represent a hydrocarbon ring.)
• n, L, ring A and ring B in formula (2) are the same as n, L, ring A and ring B in formula (1).
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-1).
• the glass transition temperature of the fluorine-containing polybenzoxazole of the present disclosure is preferably 50 to 400°C, more preferably 100 to 350°C, still more preferably 150 to 260°C.
• the glass transition temperature is a value measured by differential scanning calorimetry (DSC), dynamic viscoelasticity measurement (DMA) or thermomechanical analysis (TMA).
• the average degree of polymerization of the repeating unit represented by formula (2) is preferably 200 or less, more preferably 100 or less, and may be 2 or more, or 3 or more.
• the average degree of polymerization is calculated from the number average molecular weight (Mn) of the fluorine-containing polybenzoxazole of the present disclosure. Since the dielectric constant and dielectric loss tangent of fluorine-containing polybenzoxazole can be further lowered, the fluorine-containing polybenzoxazole may be a polymer having a relatively high average degree of polymerization, for example, an average degree of polymerization exceeding 100. may be a polymer of
• the number average molecular weight (Mn) of the fluorine-containing polybenzoxazole of the present disclosure is preferably 10,000 or more, more preferably 20,000 or more, and preferably 1,000,000 or less in terms of standard polystyrene by gel permeation chromatography. Yes, more preferably 500,000 or less.
• the molecular weight distribution (Mw/Mn) of the fluorine-containing polybenzoxazole of the present disclosure is preferably 2 or more, preferably 5 or less, and more preferably 4 or less in terms of standard polystyrene by gel permeation chromatography.
• the logarithmic viscosity ⁇ inh of the fluorine-containing polybenzoxazole of the present disclosure is preferably 0.3 dL/g or more, more preferably 0.5 dL/g or more.
• the logarithmic viscosity ⁇ inh is obtained by dissolving fluorine-containing polybenzoxazole in a solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a solution with a solution concentration of 0.5 g/dL, can be calculated by the following formula.
• Logarithmic viscosity ⁇ inh ln (solution viscosity/solvent viscosity)/solution concentration
• the fluorine-containing polyamide compound of the present disclosure is represented by the fluorinated compound (3) and the formula (4) obtained after producing the fluorinated compound (3) represented by the formula (3) by the production method described later. It can be suitably produced by polymerizing the compound (4).
• n is an integer of 1 to 8
• ring A is a hydrocarbon ring
• R 1 is independently OH, an optionally substituted linear or branched alkoxy group , represents an optionally substituted aromatic oxy group or a halogen atom.
• n and ring A in formula (3) are the same as n and ring A in formula (1).
• R 1 in formula (3) is independently OH, an optionally substituted linear or branched alkoxy group, an optionally substituted aromatic oxy group, or It is a halogen atom.
• the alkoxy group as R 1 preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
• the substituents that the alkoxy group and the aromatic oxy group as R 1 may have are preferably an alkoxy group, an alkyl group, a fluorinated alkyl group, a halo group (halogen atom), a nitro group, a cyano group or an ester group. groups are more preferred.
• Examples of the aromatic oxy group for R 1 include an optionally substituted phenoxy group and an optionally substituted triazinyloxy group.
• R 1 is independently OH, an optionally substituted phenoxy group, a methoxy group, an ethoxy group, a chlorine atom, or is preferred.
• a compound represented by formula (3-1a) or (3-1b) is more preferable.
• L and ring B in formula (4) are the same as L and ring B in formula (1).
• the polymerization of fluorinated compound (3) and compound (4) can be carried out in a solvent.
• the solvent does not substantially react with the fluorinated compound (3) and the compound (4), and has the property of well dissolving the fluorinated compound (3) and the compound (4). and a good solvent for the compound obtained by polymerization of compound (4).
• solvents include, but are not limited to, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU), dimethylsulfone, sulfolane, tetrahydrofuran (THF), cyclopentanone, cyclohexanone, acetone and the like. be done.
• DMSO dimethylsulfoxide
• DMF N,N-dimethylformamide
• DMAc N,N-dimethylacetamide
• NMP N-methyl-2-pyrrolidone
• DI 1,3-dimethylimidazolidone
• TNU tetramethylurea
• DMPU dimethylsulfone, sulfolane
• NMP N-methyl-2-pyrrolidone
• DMI 1,3-dimethylimidazolidone
• the amount of these solvents to be used is generally 10-1000 mL, preferably 50-400 mL, per 0.1 mol of fluorinated compound (3) or compound (4).
• Polymerization can also be carried out in the presence of additives.
• inorganic salts such as lithium chloride and calcium chloride may be added in order to obtain a compound with a large molecular weight.
• Lithium chloride is particularly preferred as the additive.
• the amount of additive added is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the amount of solvent.
• a silylating agent such as trialkylsilyl chloride, N,O-bis(trimethylsilyl)acetamide (BSA), N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) is added. You can BSA is particularly preferred as the silylating agent.
• the amount of the silylating agent to be added is preferably 4-fold molar amount or less, more preferably 1 to 2-fold molar amount, relative to compound (4).
• Polymerization is carried out, for example, by dissolving either one of fluorinated compound (3) and compound (4) in a solvent, adding the other compound to the resulting solution, and then stirring under an inert atmosphere such as nitrogen. It can be performed by reacting while
• the polymerization temperature is preferably -50 to 100°C, more preferably -10 to 80°C.
• the polymerization time is preferably 0.1 to 50 hours, more preferably 1 to 24 hours.
• the average degree of polymerization of the repeating unit represented by the formula (1) can be adjusted by changing the molar ratio of the fluorinated compound (3) and the compound (4), the polymerization temperature, the polymerization time, the concentration of the polymerization solution, and the like. can be done.
• a solution of a fluorine-containing polyamide compound is usually obtained by the above production method.
• the obtained solution of the fluorine-containing polyamide compound may be used as it is for various purposes. Further, after the obtained solution of the fluorine-containing polyamide compound is put into a poor solvent such as methanol or water to separate the fluorine-containing polyamide compound, the compound is purified by a reprecipitation method to remove by-products and inorganic salts. Thereby, a fluorine-containing polyamide compound having high purity may be obtained.
• the fluorinated compound (3) is a compound (7) represented by the formula (7) by reacting the compound (5) represented by the formula (5) with the compound (6) represented by the formula (6). After obtaining, the fluorinated compound (3) in which R 1 is OH can be produced by oxidizing the obtained compound (7).
• Formula (6) I-(CF 2 ) n -I (In formula (6), n is the same as in formula (3).)
• Formula (7) (In formula (7), n and ring A are the same as in formula (3).)
• Compound (5) is preferably a compound represented by formula (5-1), more preferably 4-iodotoluene or 3-iodotoluene.
• Formula (5-1) is preferably a compound represented by formula (5-1), more preferably 4-iodotoluene or 3-iodotoluene.
• Compound (7) is preferably a compound represented by formula (7-1).
• Formula (7-1) (In formula (7-1), n is the same as in formula (3).)
• Compound (7) is more preferably a compound represented by formula (7-1a) or (7-1b).
• R 1 a fluorinated compound (3) in which R 1 is OH
• a compound (8) represented by formula (8) a desired group represented by R 1 (e.g., an alkoxy group, an aromatic fluorinated compounds (3) having an oxy group) can be prepared.
• R-OH In formula (8), R is an optionally substituted linear or branched alkyl group or an optionally substituted aromatic group.
• the fluorinated compound (3) in which R 1 is a halogen atom can be produced by reacting the fluorinated compound (3) in which R 1 is OH with a halogenating agent.
• the fluorinated compound (3) in which R 1 is a triazinyloxy group can be produced by reacting the fluorinated compound (3) in which R 1 is OH with a triazine chloride compound.
• the reaction between compound (5) and compound (6) is carried out, for example, by dissolving either one of compound (5) and compound (6) in a solvent, adding the other compound to the resulting solution, and then adding nitrogen or the like. It can be carried out by reacting while stirring in an inert atmosphere.
• the reaction temperature is preferably 50 to 150°C, more preferably 100 to 140°C.
• the reaction time is preferably 0.5 to 50 hours, more preferably 1 to 30 hours.
• reaction between compound (5) and compound (6) may be carried out in the presence of a catalyst such as copper or a copper compound by adding a base such as 2,2'-bipyridyl.
• Compound (7) can be oxidized using an oxidizing agent such as CrO 3 and KMnO 4 . Moreover, the oxidation of compound (7) is preferably carried out in the presence of an acidic compound such as sulfuric acid or acetic acid.
• an oxidizing agent such as CrO 3 and KMnO 4 .
• the oxidation of compound (7) is preferably carried out in the presence of an acidic compound such as sulfuric acid or acetic acid.
• halogenating agent used in the reaction between the fluorinated compound (3) in which R 1 is OH and the halogenating agent include thionyl chloride, phosphorus trichloride and phosphorus pentachloride.
• the reaction temperature may be, for example, 20-100°C.
• Solvents include ether solvents such as diethyl ether and tetrahydrofuran.
• the reaction between the fluorinated compound (3) wherein R 1 is OH and the triazine chloride compound can be carried out in the presence of N-methylmorpholine (NMM) in a solvent, and this reaction yields a triazine-based active diester can be synthesized.
• the solvent does not substantially react with the fluorinated compound (3), the chlorinated triazine compound and N-methylmorpholine (NMM) and reacts with the fluorinated compound (3), the chlorinated triazine compound and N-methylmorpholine (NMM).
• NMM N-methylmorpholine
• solvents examples include, but are not limited to, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidone (DMI), sulfolane, tetrahydrofuran (THF), acetone and the like.
• DMSO dimethylsulfoxide
• DMF N,N-dimethylformamide
• DMAc N,N-dimethylacetamide
• NMP N-methyl-2-pyrrolidone
• DI 1,3-dimethylimidazolidone
• sulfolane tetrahydrofuran
• THF tetrahydrofuran
• acetone acetone and the like.
• N-methyl-2-pyrrolidone (NMP) is preferred.
• the amount of these solvents to be used is generally 10-1000 mL, preferably 50-
• the reaction between the fluorinated compound (3) in which R 1 is OH and the chlorinated triazine compound is carried out by, for example, dissolving either one of the fluorinated compound (3) in which R 1 is OH and the chlorinated triazine compound in a solvent, It can be carried out by adding the other compound to the obtained solution and then reacting it while stirring under an inert atmosphere such as nitrogen.
• the reaction temperature is preferably 50 to 150°C, more preferably 100 to 140°C.
• the reaction time is preferably 0.5 to 50 hours, more preferably 1 to 30 hours.
• the fluorine-containing polybenzoxazole of the present disclosure can be suitably produced by obtaining a fluorine-containing polyamide compound by the production method described above and then dehydrating and cyclizing the fluorine-containing polyamide compound. Further, when the fluorinated compound (3) and the compound (4) are polymerized in a heated state in the production of the fluorine-containing polyamide compound, part or all of the compound undergoes cyclodehydration to form the formula A compound having the repeating unit represented by (2) is formed, and as a result, the fluorine-containing polybenzoxazole of the present disclosure may be obtained as part or all of the product.
• the present disclosure also includes mixtures of fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles.
• the cyclodehydration of the fluorine-containing polyamide compound can be carried out by heating the fluorine-containing polyamide compound.
• the heating temperature for cyclodehydration is preferably 110 to 450°C, more preferably 150 to 400°C.
• the heating time is preferably 0.1 to 10 hours, more preferably 0.5 to 8 hours.
• Cyclodehydration can be carried out in air, in a nitrogen or argon atmosphere, or under reduced pressure.
• the fluorine-containing polyamide compound and fluorine-containing polybenzoxazole of the present disclosure have a low dielectric constant and a low dielectric loss tangent, and thus can be suitably used as a low dielectric material.
• the fluorine-containing polyamide compound and fluorine-containing polybenzoxazole of the present disclosure have a low dielectric constant and a low dielectric loss tangent, and can be suitably used as insulating materials for printed circuit boards.
• fluorine-containing polyamide compound and fluorine-containing polybenzoxazole of the present disclosure have a low dielectric constant and a low dielectric loss tangent, they can be , metal wiring, cover materials such as chip members such as IC chips, liquid crystal displays, organic electroluminescence displays, electronic paper, materials for electronic components and electronic equipment such as base materials for solar cells.
• the fluorine-containing polyamide compound and fluorine-containing polybenzoxazole of the present disclosure have a particularly low dielectric constant and a low dielectric loss tangent at high frequencies. It can be suitably used as a material of the type. For example, it can be suitably used as a material for insulating plates of high-frequency circuits, insulating materials for connection parts, printed circuit boards, bases and antenna covers for high-frequency vacuum tubes, coaxial cables, coated wires such as LAN cables, and the like. In addition, it can be suitably used as a material for devices such as satellite communication devices and mobile phone base stations that use microwaves of 3 to 30 GHz.
• the printed circuit board is not particularly limited, but examples include printed wiring boards for electronic circuits such as mobile phones, various computers, and communication equipment.
• the coaxial cable is not particularly limited, for example, one having a structure in which an inner conductor, an insulating coating layer, an outer conductor layer and a protective coating layer are laminated in order from the core to the outer periphery can be mentioned.
• the fluorine-containing polyamide compound and fluorine-containing polybenzoxazole of the present disclosure have a low dielectric constant and a low dielectric loss tangent, are excellent in heat resistance, solvent solubility, electrical insulation and flexibility, and can be easily formed into a thin film. Therefore, it can be suitably used for films, resist materials, and the like. Above all,
• the film can be produced by molding the fluorine-containing polyamide compound or fluorine-containing polybenzoxazole of the present disclosure by a known film molding method such as extrusion molding, calender molding, or solution casting. Further, by casting and heating a solution containing the fluorine-containing polyamide compound of the present disclosure, it is possible to simultaneously produce a fluorine-containing polybenzoxazole by cyclodehydration of the fluorine-containing polyamide compound and form a film. Furthermore, the film may be subjected to sandblasting, corona treatment, plasma treatment, etching treatment, or the like.
• m-iodotoluene (2.18 g, 10 mmol) and DMSO (4 mL) were added and dissolved in a 100 mL three-necked flask equipped with a stirrer, condenser, and nitrogen inlet tube.
• 1,6-diiodoperfluorohexane (2.79 g, 5 mmol) and copper powder (3.43 g, 54 mmol) were added, the temperature was raised stepwise to 120° C., and the reaction was allowed to proceed at 120° C. for 24 hours. rice field. After completion of the reaction, the mixture was allowed to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was distilled off under reduced pressure.
• the resulting crude product was dissolved in diethyl ether (100 mL) and washed with distilled water. The organic layer was separated and dried over anhydrous sodium sulfate overnight. A liquid product was obtained by distilling off the diethyl ether with an evaporator. Vacuum distillation (150° C./0.8 Torr) gave a clear, colorless liquid. The yield was 1.3 g (55% yield).
• P-6PFBT (10.61 g, 22 mmol), acetic acid (180 mL), and concentrated sulfuric acid (18 mL) were added to a 500 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a dropping funnel, and dissolved at 0°C. cooled.
• the reaction solution was poured into distilled water (1 L) to precipitate the product, and the white powdery product was collected by suction filtration and dried under reduced pressure at 80° C. for 12 hours.
• the dried product was recrystallized with a mixed solvent of DMF and distilled water, and dried under reduced pressure at 100° C. for 12 hours to obtain white powder crystals.
• the yield was 9.7 g (81% yield).
• reaction solution was poured into distilled water (500 mL) to precipitate the product, and the white powdery product was collected by suction filtration and dried under reduced pressure at 80° C. for 12 hours.
• the yield was 1.0 g (83% yield) and the melting point was 269-270°C.
• p-6PFBBA (5.38 g, 9.9 mmol) and thionyl chloride (40 mL) were added to an eggplant flask (100 mL) equipped with a stirrer, condenser, and calcium chloride tube. After that, the temperature was slowly raised to 85° C. and the mixture was stirred for 1 hour. After allowing to cool to room temperature, excess thionyl chloride was distilled off under reduced pressure to obtain a solid product. This was purified by sublimation (140° C./0.8 Torr) to obtain white needle crystals (yield: 4.4 g, yield: 77%). The melting point was 129-130°C.
• p-6PFBBA 27.11 g, 50 mmol
• chlorodimethoxytriazine CDMT
• NMP 400 mL
• p-6PFBBA 27.11 g, 50 mmol
• CDMT chlorodimethoxytriazine
• NMP 400 mL
• p-6PFBBA 27.11 g, 50 mmol
• CDMT chlorodimethoxytriazine
• NMP 400 mL
• reaction solution was allowed to cool to room temperature, and the reaction solution was poured into distilled water (600 mL) to precipitate the product and copper powder.
• the precipitate was collected by suction filtration and dried under reduced pressure at 60° C. for 12 hours.
• Toluene (100 mL) was added to the dried precipitate, the mixture was heated under reflux, copper powder was removed by hot filtration, and toluene was distilled off from the filtrate to obtain p-6FDEt. This was recrystallized with toluene to obtain white plate crystals.
• the yield was 1.36 g (63% yield) and the melting point was 100-101°C.
• p-iodobenzonitrile (1.82 g, 7.9 mmol) and DMSO (20 mL) were added and dissolved in a 100 mL three-necked flask equipped with a stirrer, condenser, and nitrogen inlet tube. Then add 1,6-diiodoperfluorohexane (2.20 g, 4.0 mmol), 2,2′-bipyridyl (0.25 g, 1.6 mmol) and copper powder (2.52 g, 40 mmol), The temperature was raised stepwise to 120° C. and the reaction was carried out at 120° C. for 24 hours.
• reaction solution was allowed to cool to room temperature, and the reaction solution was poured into distilled water (600 mL) to precipitate the product and copper powder.
• the precipitate was collected by suction filtration and dried under reduced pressure at 60° C. for 12 hours.
• Toluene (100 mL) was added to the dried precipitate, the mixture was heated under reflux, copper powder was removed by hot filtration, and toluene was distilled off from the filtrate to obtain p-6FDCN. This was recrystallized with toluene to obtain white crystals.
• the yield was 0.78 g (39% yield) and the melting point was 154-155°C.
• the polymerization solution was poured into distilled water (400 mL) to precipitate a fluorinated polyamide compound (p-6PFBBC/6FAP).
• the precipitated polyamide was recovered by suction filtration and dried under reduced pressure at 80° C. for 12 hours. Yield was 1.24 g (75% yield).
• a 20 wt % solution was prepared by dissolving the polyamide in NMP purified by distillation. This solution was cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours, then at 60°C for 3 hours, 100°C for 3 hours, 150°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, and 300°C for 1 hour under reduced pressure.
• a brown transparent cast film (thickness: 30 ⁇ m) was obtained by heat treatment.
• a stirrer was placed in a three-necked flask (100 mL) equipped with a nitrogen introduction tube, heated with a heat gun and dried, then 6FAP (0.70 g, 1.9 mmol) and distilled NMP (5 mL) were added and dissolved by stirring. .
• the silylating agent BSA (0.77 g, 3.8 mmol) was added and reacted at room temperature for 1 hour.
• the reaction solution was solidified with liquid nitrogen, p-4PFBBC (0.91 g, 1.9 mmol) was added, and the mixture was stirred at room temperature for 8 hours to react.
• the polymerization solution was poured into distilled water (400 mL) to precipitate a fluorinated polyamide compound (p-4PFBBC/6FAP).
• the precipitated polyamide was recovered by suction filtration and dried under reduced pressure at 80° C. for 12 hours.
• Polyamide was dissolved in distilled NMP to prepare a 20 wt% solution and cast onto a glass plate. This was dried at room temperature under reduced pressure for 3 hours, then at 60°C for 3 hours, 100°C for 3 hours, 150°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, and 300°C for 1 hour.
• a brown transparent cast film (thickness: 26 ⁇ m) was obtained by heat treatment below.
• a stirrer was placed in a three-necked flask (100 mL) equipped with a nitrogen introduction tube, heated with a heat gun and dried, then HAB (0.41 g, 1.9 mmol) and distilled NMP (5 mL) were added and dissolved by stirring. .
• the silylating agent BSA (0.77 g, 3.8 mmol) was added and reacted at room temperature for 1 hour.
• the reaction solution was solidified with liquid nitrogen, p-6PFBBC (1.10 g, 1.9 mmol) was added, and the mixture was stirred at room temperature for 8 hours to obtain a solution of a fluorinated polyamide compound (p-6PFBBC/6FAP).
• the polymerization solution was cast on a glass plate and subjected to vacuum at room temperature for 3 hours, 60°C for 3 hours, 100°C for 3 hours, 150°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, A brown cast film (thickness: 24 ⁇ m) of fluorinated polybenzoxazole (p-6PFBBC/HAB) was obtained by heat treatment at 300° C. for 1 hour and 400° C. for 30 minutes.
• a polyamide was synthesized in the same manner and heat-treated at 300°C for 1 hour to produce a polybenzoxazole film (brown transparent, thickness 35 ⁇ m).
• m-6PFBBC instead of p-6PFBBC in Example 3, a polyamide was synthesized in the same manner, and heat-treated at 350°C for 1 hour to prepare a polybenzoxazole film (brown transparent, thickness 40 ⁇ m).
• p-6PFBBC 50 mol% and m-6PFBBC (50 mol%) were used to synthesize polyamide in the same manner, and a polybenzoxazole film was formed by heat treatment at 300 ° C. for 1 hour. (brown transparent, thickness 28 ⁇ m) was produced.
• polyamide The properties of polyamide are as follows. Logarithmic viscosity ( ⁇ inh ): 0.32 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30°C)
• a polyamide was synthesized in the same manner, and heat-treated at 350° C. for 1 hour to prepare a polybenzoxazole film (pale yellow transparent, thickness 58 ⁇ m). .
• the properties of polyamide are as follows. Logarithmic viscosity ( ⁇ inh ): 0.58 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30°C) Number average molecular weight (Mn): 51,000 Weight average molecular weight (Mw): 97,000 Molecular weight distribution (Mw/Mn): 1.9
• the properties of polyamide are as follows. Logarithmic viscosity ( ⁇ inh ): 0.53 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30°C) Number average molecular weight (Mn): 50,000 Weight average molecular weight (Mw): 115,000 Molecular weight distribution (Mw/Mn): 2.3

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=85240804

Family Applications (1)

Country Status (5)

Citations (5)

Family Cites Families (2)

• 2022
  • 2022-08-15 WO PCT/JP2022/030862 patent/WO2023022123A1/ja not_active Ceased
  • 2022-08-15 JP JP2023542395A patent/JPWO2023022123A1/ja active Pending
  • 2022-08-15 EP EP22858444.7A patent/EP4389800A4/en active Pending
  • 2022-08-15 CN CN202280054806.1A patent/CN117940487A/zh active Pending
• 2024
  • 2024-02-15 US US18/442,500 patent/US20240209153A1/en active Pending

Patent Citations (5)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events