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  • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
  • C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
  • C07C215/70—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with rings other than six-membered aromatic rings being part of the carbon skeleton
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  • 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
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  • 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
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  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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  • 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
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  • 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
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

• the present invention relates to a novel fluorine-containing polymer compound useful as a material for a protective film for an electronic circuit substrate, a protective film for a semiconductor, or a gas separation film. Furthermore, the present invention relates to a fluorine-containing polymerizable monomer for producing the fluorine-containing polymer compound.
• the aromatic diamine compound is useful as a raw material for heat resistant polymers represented by polyamide, polyimide, polybenzoxazole and the like.
• These polymer materials are used in fields such as automobiles, aerospace, and fire protection clothing because of their high heat resistance.
• these polymer materials often have poor solubility in organic solvents and poor moldability. Therefore, in the case of polyimide or polybenzoxazole, after forming into a desired shape using an organic solvent-soluble precursor polymer (polyamide acid, polyamide phenol), dehydration cyclization is performed at a high temperature of 300 ° C. to 350 ° C. The final molded body is modified by polyimide or polybenzoxazole.
• the molding process as described above is a molding process for use in display members using organic dyes that have relatively low heat resistance and laminated members for semiconductors having different thermal expansion coefficients that are likely to generate residual thermal stress. Unsuitable because the temperature is too high. Therefore, organic solvent-soluble polyimides and polybenzoxazoles that can be molded at a temperature at which the organic solvent is evaporated are attracting attention.
• a bent structure such as an ether bond or a methylene bond is introduced into the main chain skeleton, and a bulky structure such as a tert-butyl group or a trifluoromethyl group is used as a side chain. It is known to introduce and destroy the symmetry of the main chain skeleton. Among them, a technique using a fluorene structure is known as a technique for improving the solubility in organic solvents without sacrificing heat resistance.
• Patent Documents 1 and 2 Polymers having a fluorene structure are not only solubilized in organic solvents, but also have the effect of lowering the dielectric constant and increasing gas permeability due to their unique structure.
• Patent Documents 1 and 2 There are examples of reports as protective films for semiconductors and gas separation films.
• a polymer having a fluorene structure has drawbacks that it is highly hydrophobic and has poor applicability to a hydrophilic substrate and poor mechanical strength due to low intermolecular interaction.
• a hydrophilic group such as phenolic hydroxyl group or carboxyl group
• a synthesis process for introducing a hydrophilic group such as phenolic hydroxyl group or carboxyl group Is multistage and the operation is complicated Patent Documents 3, 4, and 8).
• Patent Document 3 discloses a method for producing a phenolic hydroxyl group-containing fluorenediamine.
• this production method after introducing a phenolic hydroxyl group into the fluorene skeleton, nitration followed by a hydrogen reduction step yields the objective phenolic hydroxyl group-containing fluorenediamine.
• each process has a target with a relatively high yield (85 to 90%), but there is a problem of waste due to the use of a large amount of nitric acid, use of an expensive palladium catalyst, high pressure Hydrogen is necessary and it is difficult to say that it is an industrially easy method.
• Patent Document 4 discloses a method for producing a carboxyl group-containing fluorenediamine.
• diphenic acid is heated in sulfuric acid to form fluorenone carboxylic acid, and subsequently a target carboxy group-containing fluorenediamine is obtained by a reaction at a high temperature that requires a dehydration step with anilines.
• This reaction also requires a problem of waste due to the use of a large amount of sulfuric acid, and an additional facility for co-dehydration in the presence of toluene in the dehydration process, which is also not an industrially easy method.
• Patent Document 8 discloses a method for producing a phenolic hydroxyl group-containing fluorenediamine in which the substitution positions of a phenolic hydroxyl group and an amino group are reversed as compared with Patent Document 3.
• this production method general-purpose 2-benzoxazoline is used.
• separation and purification operations from by-products by silica gel chromatography are necessary, which is not an industrially easy method.
• Japanese Patent Laid-Open No. 11-343414 Japanese Unexamined Patent Publication No. 63-190607 JP 2002-105034 A JP 05-194338 A JP 2007-119503 A JP 2007-119504 A JP 2008-150534 A JP 2009-235048 A
• the present invention relates to an aromatic diamine compound having a fluorene structure and a 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl group (hereinafter referred to as “HFIP group” or “—C (CF 3 ) 2 OH”.
• HFIP group-containing fluorenediamine having introduced thereinto
• polyamide compounds, polyimide compounds, and fluorine-containing heterocyclic-containing polymer compounds having a polybenzoxazole-like structure synthesized from HFIP group-containing fluorenediamine. provide.
• a hydrophilic group such as a phenolic hydroxyl group or a carboxyl group
• a hydrophilic group such as a phenolic hydroxyl group or a carboxyl group
• the HFIP group can be introduced into the fluorene skeleton.
• the present inventors synthesized a fluorine-containing heterocyclic ring-containing polymer compound having a polyamide compound, a polyimide compound, and a polybenzoxazole-like structure from an HFIP group-containing fluorenediamine to complete the present invention.
• the present invention is as follows.
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group,
• the fluorine-containing fluorenediamine according to invention 1 represented by formula (3-1): (Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C ⁇ C—C (CH 3 ) 2 OH group, —C ⁇ C—
• the fluorine-containing diamine according to any one of the inventions 1 to 3 is a dicarboxylic acid or dicarboxylic acid derivative represented by the formula (10) or (11), or a tetracarboxylic dianhydride represented by the formula (14).
• A is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom, Any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and each R 4 is independently a hydrogen atom or a carbon number of 1 to 10
• A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and is an oxygen atom, a sulfur atom, or a nitrogen atom.
• R 5 is a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom and a nitrogen atom.
• any number of hydrogen atoms may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, or a cyano group.
• a polymer compound containing at least a repeating unit represented by formula (6) (Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C ⁇ C—C (CH 3 ) 2 OH group, —C ⁇ C—C 6 H
• the polymer compound according to invention 5 comprising at least a repeating unit represented by formula (19).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group,
• the polymer compound according to invention 5 or 6, comprising at least a repeating unit represented by formula (6A).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• 1 represents a substituent selected from the group consisting of phenyl group, methoxy group and nitro group
• A is a divalent organic group containing one or more selected from alicyclic, aromatic and alkylene groups
• oxygen May contain atoms, sulfur atoms, or nitrogen atoms, and any number of hydrogen atoms may be substituted with alkyl groups, fluorine atoms, chlorine atoms, fluoroalkyl groups, carboxyl groups, hydroxy groups, or cyano groups
• HFIP represents a —C (CF 3 )
• [Invention 8] A polymer compound containing at least a repeating unit represented by formula (9).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• 1 represents a substituent selected from the group consisting of a group, a phenyl group, a methoxy group, and a nitro group
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, or a biphenyl group.
• Sulfonic acid group —C ⁇ C—C (CH 3 ) 2 OH group, —C ⁇ C—C 6 H 5 group, —C ⁇ C—Si (CH 3 ) 3 group
• A represents a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom;
• the number of hydrogen atoms is an alkyl group, a fluorine atom, a chlorine atom, Kill group, a carboxyl group, may be substituted by a hydroxy group or a cyano group.
• the polymer compound according to invention 8 which contains at least a repeating unit represented by formula (9B).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• 1 represents a substituent selected from the group consisting of a group, a phenyl group, a methoxy group, and a nitro group
• A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, It may contain oxygen, sulfur, or nitrogen atoms, and any number of hydrogen atoms are substituted with alkyl, fluorine, chlorine, fluoroalkyl, carboxyl, hydroxy or cyano groups May be good.
• a polymer compound containing at least a repeating unit represented by formula (7) (Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C ⁇ C—C (CH 3 ) 2 OH group, —C ⁇ C—C 6 H
• Any number of hydrogen atoms may be alkyl groups, fluoroalkyl Optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group, m and n each independently represents an integer of 0 to 2; m + n is 1 or more and 4 or less.
• the polymer compound according to invention 10 comprising at least a repeating unit represented by formula (7A).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group,
• Any number of hydrogen atoms may be alkyl groups, fluoroalkyl And optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group.
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 5 represents a tetravalent organic group containing one or more substituents selected from the group consisting of a phenyl group, a methoxy group and a nitro group, wherein R 5 is one or more selected from an alicyclic ring, an aromatic ring and an alkylene group; Fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom may be contained, and any number of hydrogen atoms may be substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano
• a polymer compound containing at least a repeating unit represented by formula (8) (Wherein R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms) Represents a substituent selected from the group consisting of a phenyl group, a methoxy group, and a nitro group, and R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group, One kind selected from the group consisting of a sulfonic acid group, —C ⁇ C—C (CH 3 ) 2 OH group, —C ⁇ C—C 6 H
• Any number of hydrogen atoms may be alkyl groups, fluoroalkyl Optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group, m and n each independently represents an integer of 0 to 2; m + n is 1 or more and 4 or less.
• the polymer compound according to invention 13 comprising at least a repeating unit represented by formula (8A).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group,
• Any number of hydrogen atoms may be alkyl groups, fluoroalkyl And optionally substituted with a group, a carboxyl group, a hydroxy group or a cyano group, HFIP represents a —C (CF 3 ) 2 OH group.
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 5 represents a tetravalent organic group containing one or more substituents selected from the group consisting of a phenyl group, a methoxy group and a nitro group, wherein R 5 is one or more selected from an alicyclic ring, an aromatic ring and an alkylene group; Fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom may be contained, and any number of hydrogen atoms may be substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano
• an HFIP group-containing fluorenediamine Furthermore, according to the present invention, it is possible to provide a polyamide compound, a polyimide compound, and a fluorine-containing heterocyclic-containing polymer compound having a polybenzoxazole-like structure synthesized from HFIP group-containing fluorenediamine.
• 9,9-bis (4-aminophenyl) fluorene represented by the following formula (1) is referred to as “fluor orange amine”. It may have a substituent. However, when it has a HFIP group as a substituent, it distinguishes and calls as "HFIP group containing fluorene amine”.
• HFIP group-containing fluoreneamine according to the present invention, HFIP group-containing fluoreneamine as monomers, polyamide compound obtained by polymerization reaction, polyimide compound, fluorine-containing heterocyclic ring-containing polymer compound having a polybenzoxazole-like structure in this order It explains along.
• the HFIP group-containing fluorenediamine according to the present invention is represented by the formula (2).
• R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a naphthyl group, a biphenyl group,
• HFIP group-containing fluorenediamine (2) the compounds represented by the formulas (3-1) and (3-2) HFIP group-containing fluorenediamine is preferred.
• R 1 , R 2 and HFIP have the same meaning as in formula (2).
• alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
• fluoroalkyl group having 1 to 4 carbon atoms in which any number of hydrogen atoms are substituted with fluorine atoms include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl Group, perfluoro tert-butyl group and the like.
• HFIP group-containing fluorenediamine examples include compounds represented by the following formulas (4-1) to (4-12).
• R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Me represents a methyl group.
• Ph represents a phenyl group.
• HFIP has the same meaning as in formula (2).
• the HFIP group-containing fluorenediamines represented by the general formulas (4-1) and (4-2) are particularly preferable because of the availability of fluoreneamine as a raw material for synthesizing the HFIP group-containing fluorenediamine.
• the HFIP group-containing fluorenediamine (2) according to the present invention is obtained by replacing fluorediamine represented by the formula (5) (hereinafter sometimes referred to as “fluorangeamine” (5)) with hexafluoroacetone or hexafluoroacetone. -It is obtained by making it react with a trihydrate (refer patent document 5, 6, 7). (In formula (5), R 1 and R 2 have the same meaning as in formula (2).)
• This reaction can be carried out without solvent, but a solvent can also be used.
• the solvent used is not particularly limited as long as it does not participate in the reaction, but is preferably an aromatic hydrocarbon such as xylene, toluene, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, or water.
• the amount of the solvent to be used is not particularly limited, but it is not preferable to use a large amount because the yield per volume decreases.
• the reactor to be used is not particularly limited. However, when a sealed reactor (autoclave) is used, the mode differs depending on whether hexafluoroacetone or hexafluoroacetone trihydrate is used. . In the case of using hexafluoroacetone, first, fluorenediamine (5) and, if necessary, a catalyst and / or a solvent are charged into the reactor. Subsequently, it is preferable to introduce hexafluoroacetone successively while raising the temperature so that the internal pressure of the reactor does not exceed 0.5 MPa.
• the reaction time of this reaction is not particularly limited, but the optimum reaction time varies depending on the temperature and the amount of catalyst used. Therefore, it is preferable to complete this step after confirming that the raw material has been sufficiently consumed by carrying out the reaction while measuring the progress of the reaction by a general-purpose analysis means such as gas chromatography.
• the HFIP group-containing fluorenediamine (2) can be obtained by ordinary means such as extraction, distillation, and crystallization. Moreover, it can also refine
• polyamide compound (6) a polyamide compound containing at least a repeating unit represented by the general formula (6) obtained by a polymerization reaction
• polyamide compound (7) a polyamide compound containing at least the repeating unit represented by the general formula (7)
• polyimide compound (8) A polymer compound such as a polyimide compound containing at least a repeating unit (hereinafter sometimes referred to as “polyimide compound (8)”) will be described in order.
• fluorine-containing heterocyclic ring-containing polymer compound having a polybenzoxazole-like structure containing at least the repeating unit represented by the general formula (9) hereinafter referred to as “fluorinated heterocyclic ring-containing polymer compound (9)”)
• the polyamide compound (6) is an HFIP-containing fluorenediamine (2), a carboxylic acid or a carboxylic acid represented by formula (10) or formula (11). It can be obtained by reacting with a derivative.
• R 1 , R 2 , HFIP, m and n are as defined in formula (2).
• R 4 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a benzyl group.
• dicarboxylic acid or dicarboxylic acid derivative represented by the general formulas (10) and (11) any of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, or these dicarboxylic acid derivatives may be used.
• Examples of the aliphatic dicarboxylic acid and derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dicarboxylic acid compounds of sebacic acid or their dicarboxylic acid derivatives. It is done.
• aromatic dicarboxylic acids and derivatives thereof include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-dicarboxybiphenyl, 3,3′-dicarboxybiphenyl, 3,3′-dicarboxyldiphenyl ether, 3, 4'-dicarboxyldiphenyl ether, 4,4'-dicarboxyldiphenyl ether, 3,3'-dicarboxyldiphenylmethane, 3,4'-dicarboxyldiphenylmethane, 4,4'-dicarboxyldiphenylmethane, 4,4'-dicarboxyldiphenylmethane, 3,3'-dicarboxyl Diphenyldifluoromethane, 3,4'-dicarboxyldiphenyldifluoromethane, 4,4'-dicarboxyldiphenyldifluoromethane, 3,3'-dicarboxyldiphenylsulfone
• terephthalic acid, isophthalic acid, 4,4′-dicarboxybiphenyl, 2,2′-ditrifluoromethyl-4 are easy to obtain, easy to polycondensation reaction, and excellent in transparency.
• 4,4′-dicarboxybiphenyl and 2,2-bis (4-carboxyphenyl) hexafluoropropane are preferred.
• a polyamide compound containing at least a repeating unit represented by any of the following formulas (12-1) to (12-5) is preferable.
• R 1 , R 2 and HFIP have the same meaning as in formula (2).
• a polyamide compound containing at least a repeating unit represented by any of the following formulas (13-1) to (13-10) can be given.
• R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group.
• HFIP has the same meaning as in formula (2).
• a polyamide compound containing at least a repeating unit represented by any one of the formulas (13-1) to (13-5) is particularly preferred because of the availability of fluoreneamine as a raw material for the synthesis of HFIP group-containing fluoreneamine. preferable.
• the weight average molecular weight of the polyamide compound (6) is preferably 10,000 or more, more preferably 20,000 or more.
• the upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less.
• the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor.
• the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.
• the weight average molecular weight here is determined as a converted value based on standard polystyrene by gel permeation chromatography (hereinafter sometimes referred to as “GPC”) analysis (the same applies hereinafter). Detailed analysis conditions for the analysis are described in the examples of the present application.
• the method for synthesizing the polyamide compound (6) is not particularly limited, and a known method for synthesizing a polyamide compound from a diamine compound and a carboxylic acid compound or a derivative thereof can be employed.
• a composition having HFIP group-containing fluorenediamine (2) and a dicarboxylic acid or dicarboxylic acid derivative represented by the general formulas (10) and (11) is melted together at 150 ° C. or higher and condensed without solvent.
• Examples thereof include a polymerization reaction method, a condensation polymerization reaction in a solvent at 150 ° C. or higher, and a polymerization reaction in a solvent at a temperature of ⁇ 20 to 80 ° C.
• a solvent can be used.
• the solvent to be used is not particularly limited as long as the reaction substrate dissolves and does not freeze at the reaction temperature, and examples thereof include amides, aromatics, halogens, lactones and the like.
• the polyamide compound (7) reacts the HFIP-containing fluorenediamine (2) with the tetracarboxylic dianhydride represented by the formula (14). Can be obtained.
• R 1 , R 2 , HFIP, m and n are as defined in formula (2).
• R 5 is a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group.
• tetracarboxylic dianhydride represented by the general formula (14)
• those having any of aliphatic, alicyclic and aromatic structures in R 5 can be used.
• benzenetetracarboxylic dianhydride pyromellitic dianhydride
• trifluoromethylbenzenetetracarboxylic dianhydride bistrifluoromethylbenzenetetracarboxylic dianhydride, difluorobenzenetetracarboxylic dianhydride
• Naphthalenetetracarboxylic dianhydride biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ketonic dianhydride, oxydiphthalic acid
• polyamide compounds (7) polyamide compounds containing at least any of the repeating units represented by the following formulas (15-1) to (15-6) are preferable.
• R 1 , R 2 and HFIP have the same meaning as in formula (2).
• Specific examples include polyamide compounds containing at least any of the repeating units represented by the following formulas (16-1) to (16-12).
• R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group.
• HFIP has the same meaning as in formula (2).
• polyamide compounds containing at least any one of the repeating units represented by the formulas (16-1) to (16-6) are obtained because of the availability of fluorenediamine as a raw material for the synthesis of HFIP group-containing fluorenediamine, Particularly preferred.
• the weight average molecular weight of the polyamide compound (7) is preferably 10,000 or more, more preferably 20,000 or more.
• the upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.
• the method for synthesizing the polyamide compound (7) is not particularly limited, and for example, a composition having a HFIP group-containing fluorenediamine (2) and a dicarboxylic acid derivative represented by the general formula (14) at 150 ° C. or higher.
• a composition having a HFIP group-containing fluorenediamine (2) and a dicarboxylic acid derivative represented by the general formula (14) at 150 ° C. or higher examples thereof include a method in which they are melted together and subjected to a polycondensation reaction without solvent, a method in which a polycondensation reaction is performed at 150 ° C. or higher in a solvent, and a method in which a polymerization reaction is performed in a solvent at a temperature of ⁇ 20 to 80 ° C.
• a solvent can be used in the synthesis of the polyamide compound (7).
• the solvent to be used is not particularly limited as long as the reaction substrate dissolves and does not freeze at the reaction temperature, and examples thereof include amides, aromatics, halogens, lactones and the like.
• the polyimide compound represented by the formula (8) is synthesized from the polyamide compound (7).
• R 1 , R 2 , HFIP, m and n are as defined in formula (2).
• R 5 is a tetravalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group. Yes, it may contain fluorine atom, chlorine atom, oxygen atom, sulfur atom, nitrogen atom, and any number of hydrogen atoms are substituted with alkyl group, fluoroalkyl group, carboxyl group, hydroxy group or cyano group May be.
• a polyimide compound containing at least any one of the repeating units represented by the following formulas (17-1) to (17-6) is preferable.
• R 1 , R 2 and HFIP have the same meaning as in formula (2).
• Specific examples include polyimide compounds containing at least one of the repeating units represented by the following formulas (18-1) to (18-12).
• R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group.
• HFIP has the same meaning as in formula (2).
• polyimide compounds containing at least any one of the repeating units represented by formulas (18-1) to (18-6) are particularly preferred because of the availability of fluoreneamine as a raw material for the synthesis of HFIP group-containing fluoreneamine. preferable.
• the weight average molecular weight of the polyimide compound (8) is preferably 10,000 or more, more preferably 20,000 or more.
• the upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.
• the synthesis reaction of the polyimide (8) that is, the dehydration cyclization reaction of the polyamide compound (7) is carried out under the condition that the reaction is promoted only by heating or by the combined use of an additive such as acid or base and heat.
• the polyamide compound (7) solution can be imidized at a high temperature of 150 ° C. or higher and 250 ° C. or lower to prepare a polyimide solution containing an HFIP group.
• pyridine, triethylamine, acetic anhydride or the like may be used as an additive.
• the concentration of the polyimide containing HFIP groups in the solution is preferably 5% by mass or more and 50% by mass or less. If it is less than 5% by mass, it is too thin to be industrially practical. If it exceeds 50% by mass, it is difficult to dissolve. Furthermore, it is preferably 10% by mass or more and 40% by mass or less.
• the solvent used in preparing the solution of the polyamide compound (7) is not particularly limited as long as the reaction substrate dissolves.
• N, N-dimethylformamide, N, N-dimethylacetamide, hexa Methylphosphoric triamide or N-methyl-2-pyrrolidone aromatic solvents benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile, halogenated solvents chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2 , 2-tetrachloroethane, lactones ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone or ⁇ -methyl- ⁇ -butyrolactone.
• These solvents may be used alone or as a mixed solvent of two or more.
• a method for synthesizing the polyimide (8) a method in which the reaction solution immediately after the synthesis of the polyamide compound (7) is directly subjected to a dehydration cyclization reaction is also applicable.
• the above-mentioned temperature range, additive, concentration and solvent can be used.
• the fluorine-containing heterocyclic ring-containing polymer compound (9) is a polyamide compound containing at least a repeating unit represented by the formula (19) (hereinafter “polyamide”).
• Compound (19) may be obtained by dehydrating cyclization.
• R 1 , R 2 and HFIP are as defined in formula (2).
• A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring and an alkylene group, It may contain a sulfur atom or a nitrogen atom, and any number of hydrogen atoms may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group.
• A is a divalent organic group containing at least one selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and any number
• the hydrogen atom may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a fluoroalkyl group, a carboxyl group, a hydroxy group or a cyano group, and the line segment intersecting with the wavy line represents the bonding position.
• a fluorine-containing heterocyclic ring-containing polymer compound containing at least any one of the repeating units represented by the following formulas (20-1) to (20-5) is preferable.
• R 1 , R 2 and HFIP have the same meaning as in formula (2).
• Specific examples include fluorine-containing heterocyclic ring-containing polymer compounds containing at least any one of the repeating units represented by the following formulas (21-1) to (21-10).
• R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Me represents a methyl group. Ph represents a phenyl group.
• a fluorine-containing heterocyclic ring containing at least any one of the repeating units represented by formulas (21-1) to (21-5) because of the availability of fluoreneamine as a raw material for the synthesis of HFIP group-containing fluorenediamine.
• the containing polymer compound is particularly preferable.
• the weight average molecular weight of the fluorine-containing heterocyclic ring-containing polymer compound (9) is preferably 10,000 or more, more preferably 20,000 or more.
• the upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 300,000 or less. When the weight average molecular weight is less than 10,000, the strength of the resulting polymer film is poor. When the weight average molecular weight is more than 500,000, the viscosity of the resulting polymer solution becomes too high and handling becomes difficult.
• reaction conditions such as heating, use of an acid catalyst, and a base catalyst can be selected.
• reaction conditions in the similar dehydration cyclization reaction disclosed in Patent Documents 6 and 7 can be applied mutatis mutandis.
• the polyamide compound (19) is heated in a solvent at 150 to 250 ° C., whereby the dehydration cyclization of the polyamide compound (19) proceeds, and the fluorine-containing heterocyclic ring-containing polymer compound (9) Produces.
• pyridine, triethylamine, acetic anhydride and the like may be added for the purpose of allowing the reaction to proceed efficiently.
• a solvent can be used.
• the solvent to be used is not particularly limited as long as the reaction substrate dissolves and does not freeze at the reaction temperature, and examples thereof include amides, aromatics, halogens, lactones and the like.
• acid acceptors such as pyridine and triethylamine
• a polyamide compound (6) for the purpose of improving the heat resistance of the polymer compound and obtaining solubility in a desired organic solvent, a polyamide compound (6), a polyamide compound (7), a polyimide obtained from the HFIP group-containing fluorenediamine (2)
• a diamine compound not containing an HFIP group may be added as a polymerization component.
• the diamine compound includes 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3′-bistrifluoromethyl-4,4′-diaminobiphenyl, 2,2′- Bistrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-bistrifluoromethyl-5,5′-diaminobiphenyl, bis (trifluoromethyl) -4,4′-diaminobiphenyl, bis (fluorinated alkyl) -4,4'-diaminobiphenyl, dichloro-4,4'-diaminobiphenyl, dibromo-4,4'-diaminobiphenyl, bis (fluorinated alkoxy) -4,4'-diaminobiphenyl, diphenyl-4,4 ' -Diaminobiphenyl, 4,4'-bis (4-aminotetrafluorophenoxy) tetrafluor
• the polymer compound of the present invention can be used in a varnish state, a powder state, a film state, or a solid state dissolved in an organic solvent.
• the obtained polymer compound may contain additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer as necessary. Absent.
• in varnish When using in varnish, apply it on a substrate such as glass, silicon wafer, metal, metal oxide, ceramics, resin, etc. by usual methods such as spin coating, spray coating, flow coating, impregnation coating, brush coating. Can do.
• the physical property evaluation of the polymer compound using the HFIP group-containing fluorenediamine and the HFIP group-containing fluorenediamine obtained in the present invention was performed by the following methods.
• NMR (nuclear magnetic resonance) measurement The structure of the compound was confirmed by 1 H-NMR and 19 F-NMR measurements using an NMR (nuclear magnetic resonance) apparatus (JNM-AL400 or JNM-ECA400; manufactured by JEOL Ltd.) having a resonance frequency of 400 MHz.
• the weight average molecular weight (hereinafter sometimes referred to as “Mw”) is a value determined by gel permeation chromatography (HLC-8320 manufactured by Tosoh Corporation, tetrahydrofuran is used) with polystyrene as a standard product.
• Example 5 ⁇ Film-forming experiment of polymer P1-1>
• the polymer P1-1 (3 g) obtained in Example 4 was dissolved in N, N-dimethylacetamide (12 g), and then the obtained solution was spin-coated on a glass substrate to obtain N, N-dimethyl.
• the upper limit temperature was 180 ° C. close to the boiling point of acetamide, and heating was performed at 100 ° C. for 1 hour and 180 ° C. for 1 hour. On the glass substrate, no peeling or cracking was observed visually, and a uniform film having a thickness of 25 ⁇ m was obtained.
• Example 8 ⁇ Film-forming experiment of polymer P2-1> After the polymer P2-1 (3 g) obtained in Example 7 was dissolved in N-methylpyrrolidone (12 g), the obtained solution was spin-coated on a glass substrate and was close to the boiling point of N-methylpyrrolidone. 200 ° C. was the upper limit temperature, and heating was performed at 100 ° C. for 1 hour and at 200 ° C. for 1 hour. On the glass substrate, no peeling or cracking was observed visually, and a uniform film having a thickness of 23 ⁇ m was obtained.
• Example 27 to 35 ⁇ Film formation experiment of polymers P3-1 to P11-1>
• the polymers P3-1 to P7-1 were spin-coated on the glass substrate by the same method as in Example 5, and the polymers P8-1 to P11-1 were formed by the same method as in Example 8. The results are shown in Table 5.
• the coating film of the HFIP group-containing polymer compound according to the present invention can be used as a coating material for a flat panel display, a protective film for a substrate body for an electronic circuit, a protective film for a semiconductor, and the like.

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