WO2015159911A1 - Resine de reserve et son procede de fabrication - Google Patents

Resine de reserve et son procede de fabrication Download PDF

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Publication number
WO2015159911A1
WO2015159911A1 PCT/JP2015/061557 JP2015061557W WO2015159911A1 WO 2015159911 A1 WO2015159911 A1 WO 2015159911A1 JP 2015061557 W JP2015061557 W JP 2015061557W WO 2015159911 A1 WO2015159911 A1 WO 2015159911A1
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acid
group
carbon atoms
anhydride
polyimide
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PCT/JP2015/061557
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English (en)
Japanese (ja)
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青木　暢章
壮 六人部
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ナガセケムテックス株式会社
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Priority to CN201580020255.7A priority Critical patent/CN106255714A/zh
Priority to KR1020167024521A priority patent/KR20160147712A/ko
Priority to JP2016513809A priority patent/JPWO2015159911A1/ja
Publication of WO2015159911A1 publication Critical patent/WO2015159911A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides

Definitions

  • the present invention relates to a novel resist resin and a method for producing the same.
  • Polyimide is widely used in the electronics field because of its excellent heat resistance and mechanical properties.
  • polyimide is often insoluble in an organic solvent.
  • a solution of a precursor polyamic acid (polyamic acid) is applied to a substrate and heated at a high temperature of 250 ° C. or higher to remove the organic solvent and imide. It was formed (film) by making.
  • this method has a drawback that the base material and peripheral materials may be deteriorated by heating at a high temperature. Therefore, polyamic acid and polyimide that can be molded at a lower temperature have been demanded.
  • Patent Document 1 discloses a silicone-modified polyimide having a glass transition point of 170 ° C. to 190 ° C.
  • a polyimide raw material has a problem that it is difficult to obtain industrially.
  • An object of this invention is to provide the polyamic acid and the polyimide which were excellent in low-temperature workability
  • the present inventors use a diamine containing a fluorene skeleton as all or part of a diamine component used when synthesizing polyamic acid and polyimide, while maintaining high heat resistance, Polyamic acid and polyimide excellent in low-temperature workability can be obtained, and the knowledge that the obtained polyimide is excellent in solvent solubility was obtained, and the present invention was completed.
  • polyamic acid and polyimide of the present invention relate to: [1] Polyamic acid represented by the following general formula (1):
  • R 1 and R 2 each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a halogen atom;
  • n represents an integer of 0 to 20;
  • Y represents a residue excluding the carboxyl group of dicarboxylic acid or the acid anhydride group of dicarboxylic anhydride; and
  • Z represents the carboxyl group of tetracarboxylic acid or the acid anhydride group of tetracarboxylic dianhydride. Represents a residue]];
  • Y is maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, and glutaric acid
  • the polyamic acid according to [1] which is a residue obtained by removing a carboxyl group of a dicarboxylic acid selected from the group consisting of: or an acid anhydride group of these acid anhydrides;
  • the polyamic acid of [1] or [2] which is a residue obtained by removing a carboxyl group of an acid or an acid anhydride group of these acid dianhydrides;
  • R 1 and R 2 each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a halogen atom;
  • n represents an integer of 0 to 20;
  • Y represents a residue excluding the carboxyl group of dicarboxylic acid or the acid anhydride group of dicarboxylic anhydride; and
  • Z represents the carboxyl group of tetracarboxylic acid or the acid anhydride group of tetracarboxylic dianhydride. Represents a residue]];
  • Y is maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, and glutaric acid
  • the polyimide according to [4] which is a residue obtained by removing a carboxyl group of a dicarboxylic acid selected from the group consisting of or an acid anhydride group of these acid anhydrides;
  • Z is selected from the group consisting of pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, oxydiphthalic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bistrimellitate, and butanetetracarboxylic acid
  • the polyimide of [4] or [5] which is a residue obtained by removing the acid carboxyl group or the acid anhydride group of these acid dianhydrides;
  • a method for producing polyimide comprising a step of ring closure after obtaining a polyamic acid by the production method of [7] or [8];
  • a resist resin composition comprising the polyamic acid according to any one of [1] to [3] and / or the polyimide according to any one of [4] to [6].
  • the present invention provides a polyamic acid and a polyimide excellent in low-temperature workability while maintaining high heat resistance. Moreover, the polyimide excellent in solvent solubility is provided.
  • polyamic acid of the present invention is represented by the following general formula (1):
  • R 1 and R 2 are not particularly limited, but each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, or Represents an arylene group having 6 to 10 carbon atoms.
  • Examples of the alkylene group having 1 to 5 carbon atoms in the general formula (1) include a methylene group, an ethylene group, a propylene group, and a trimethylene group. Preferable are a methylene group and an ethylene group.
  • Examples of the alkenylene group having 2 to 5 carbon atoms in the general formula (1) include an ethenylene group, a 2-propenylene group, a 2-butenylene group, and a 3-butenylene group. Preferably, they are an ethenylene group and a 2-propenylene group.
  • Examples of the arylene group having 6 to 10 carbon atoms in the general formula (1) include a phenylene group, an alkylphenylene group (methylphenylene group (tolylene group), dimethylphenylene group (xylylene group)) and the like. Preferably, it is a phenylene group.
  • R 3 and R 4 are not particularly limited, but each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon It represents an aryl group of formula 6 to 10, or a halogen atom.
  • Examples of the alkyl group having 1 to 5 carbon atoms in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, and a t-butyl group. Preferably, they are a methyl group and an ethyl group.
  • Examples of the alkenyl group having 2 to 5 carbon atoms in the general formula (1) include an ethenyl group, a 2-propenyl group, a 2-butenyl group, and a 3-butenyl group. Preferred are an ethenyl group and a 2-propenyl group.
  • Examples of the aryl group having 6 to 10 carbon atoms in the general formula (1) include a phenyl group, an alkylphenyl group (methylphenyl group (tolyl group), dimethylphenyl group (xylyl group)) and the like. Preferably, it is a phenyl group.
  • halogen atom in the general formula (1) examples include fluorine, chlorine, bromine, iodine and the like. Preferably, it is fluorine.
  • n represents an integer of 0 to 20. n preferably represents an integer of 1 to 5. When n is out of the above range, compatibility with other materials (components) may be reduced when a resist resin composition is used.
  • Y represents a residue (dicarboxylic acid residue) excluding the carboxyl group of dicarboxylic acid or the acid anhydride group of dicarboxylic anhydride.
  • the dicarboxylic acid or dicarboxylic acid anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellit An acid, glutaric acid, these acid anhydrides, etc. are mentioned.
  • Preferred are phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof.
  • Z represents a residue (tetracarboxylic acid residue) excluding the carboxyl group of tetracarboxylic acid or the acid anhydride group of tetracarboxylic dianhydride.
  • tetracarboxylic acid or tetracarboxylic dianhydride include aromatic polyvalent carboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, oxydiphthalic acid, diphenylsulfonetetracarboxylic acid, and ethylene glycol bistrimellitate.
  • Examples thereof include aliphatic polyvalent carboxylic acids such as acid and butanetetracarboxylic acid, and acid dianhydrides thereof.
  • Biphenyltetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bistrimellitate, and acid dianhydrides thereof are preferable.
  • polyamic acid of the present invention may partially have an imide bond.
  • the weight average molecular weight of the polyamic acid of the present invention is not particularly limited, but is preferably 500 to 15000, and more preferably 1000 to 3000. When the weight average molecular weight is out of the above range, compatibility with other materials (components) may be reduced when a resist resin composition is prepared. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography (GPC).
  • the polyimide of the present invention is obtained by ring-closing (imidizing) the polyamic acid represented by the above general formula (1), and is represented by the following general formula (2):
  • the polyamic acid of the present invention is a precursor of the polyimide of the present invention.
  • a heating or dehydrating agent By reacting in the presence of a heating or dehydrating agent, the NH group and the carboxyl group in the amide group inside the polyamic acid are dehydrated and condensed to form a ring.
  • ring closure By forming (ring closure), polyimide is formed.
  • R 1 and R 2 are not particularly limited, but each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, or Represents an arylene group having 6 to 10 carbon atoms.
  • alkylene group having 1 to 5 carbon atoms examples include those described above for the general formula (1).
  • R 3 and R 4 are not particularly limited, but each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon It represents an aryl group of formula 6 to 10, or a halogen atom.
  • Examples of the alkyl group having 1 to 5 carbon atoms, the alkenyl group having 2 to 5 carbon atoms, the aryl group having 6 to 10 carbon atoms and the halogen atom in the general formula (2) include those described above for the general formula (1). It is done.
  • n represents an integer of 0 to 20. n preferably represents an integer of 1 to 5. When n is out of the above range, compatibility with other materials (components) may be reduced when a resist resin composition is used.
  • Y represents the residue except the carboxyl group of dicarboxylic acid or the acid anhydride group of dicarboxylic anhydride.
  • Examples of the dicarboxylic acid or dicarboxylic acid anhydride in the general formula (2) include those described above for the general formula (1).
  • Z represents the residue except the carboxyl group of tetracarboxylic acid or the acid anhydride group of tetracarboxylic dianhydride.
  • examples of the tetracarboxylic acid or tetracarboxylic dianhydride in the general formula (2) include those described above for the general formula (1).
  • the weight average molecular weight of the polyimide of the present invention is not particularly limited, but is preferably 500 to 15000, more preferably 1000 to 3000. When the weight average molecular weight is out of the above range, compatibility with other materials (components) may be reduced when a resist resin composition is prepared.
  • the method for producing polyamic acid of the present invention comprises a diamine containing a fluorene skeleton, dicarboxylic acid or its acid anhydride and tetracarboxylic acid or It includes a step of reacting with the acid dianhydride.
  • the diamine containing a fluorene skeleton include 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, and 9,9-bis (4-amino). -3-fluorophenyl) fluorene and the like.
  • Preferred is 9,9-bis (4-aminophenyl) fluorene.
  • a diamine containing a fluorene skeleton and another diamine may be used in combination.
  • Other diamines that can be used in combination with a diamine containing a fluorene skeleton are not particularly limited, and examples thereof include compounds having two amino groups that can be used as a raw material for polyimide. Examples include aromatic diamines, alicyclic diamines, and fatty acids. Group diamine and the like.
  • the aromatic diamine is not particularly limited.
  • the alicyclic diamine is not particularly limited.
  • isophorone diamine 4,4′-methylenebis (4-cyclohexylamine), 1,4-diaminocyclohexane, bicyclo [2.2.1] heptanebis (methylamine) 1,3-diaminoadamantane, 1,3-bis (aminomethyl) benzene, 1,4-bis (aminomethyl) benzene and the like.
  • the aliphatic diamine is not particularly limited, and examples thereof include ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, and the like.
  • a diamine other than a diamine containing a fluorene skeleton may or may not be used in the production method of the present invention, but when used, only one type may be used or two or more types may be used. May be used in combination.
  • dicarboxylic acid or its acid anhydride As dicarboxylic acid or its acid anhydride, and tetracarboxylic acid or its acid dianhydride, what was mentioned above about General formula (1) and (2) is mentioned. As for dicarboxylic acid or its acid anhydride and tetracarboxylic acid or its acid dianhydride, only 1 type may respectively be used and 2 or more types may be used together.
  • a diamine containing a fluorene skeleton (sometimes a diamine containing a fluorene skeleton and other diamines; hereinafter, a diamine containing a fluorene skeleton and another diamine are also simply referred to as a diamine).
  • dicarboxylic acid or its acid anhydride, and tetracarboxylic acid or its acid dianhydride may be reacted with dicarboxylic acid or its acid anhydride and tetracarboxylic acid or its acid dianhydride simultaneously.
  • the resulting reaction product may be reacted with dicarboxylic acid or its acid anhydride.
  • an amino group in a diamine a total of a diamine containing a fluorene skeleton and another diamine
  • a tetracarboxylic acid or an acid dianhydride thereof a tetracarboxylic acid or an acid dianhydride thereof
  • an acid anhydride group in a dicarboxylic acid or an acid anhydride thereof are What is necessary is just to use it so that it may become substantially equimolar.
  • two carboxyl groups of tetracarboxylic acid or dicarboxylic acid correspond to one acid anhydride group.
  • the reaction of diamine with dicarboxylic acid and tetracarboxylic acid is preferably performed in the presence of a catalyst or a condensing agent.
  • the catalyst is not particularly limited, and examples thereof include pyridine and 4-dimethylaminopyridine. These may be used alone or in combination of two or more.
  • the condensing agent is not particularly limited, and examples thereof include N, N′-dicyclohexylcarbodiimide. These may be used alone or in combination of two or more.
  • the dicarboxylic acid or acid anhydride thereof and the tetracarboxylic acid or acid dianhydride preferably have a molar ratio of 1:99 to 90:10, preferably 5:95 to 80:20. A molar ratio is more preferred.
  • the organic solvent that can be used in this reaction is not particularly limited as long as it can dissolve diamine and dicarboxylic acid or acid anhydride thereof, and tetracarboxylic acid or acid dianhydride thereof.
  • aprotic polar solvents such as These may use only 1 type and may use 2 or more types together.
  • the reaction of diamine with dicarboxylic acid or acid anhydride thereof and tetracarboxylic acid or acid dianhydride is preferably performed at 30 to 70 ° C., preferably at 40 to 60 ° C. for 2 to 20 hours in an organic solvent. Can be carried out for 5 to 16 hours.
  • the method for producing a polyimide of the present invention includes a step of ring closure after obtaining a polyamic acid by the above-described production method.
  • the polyimide of the present invention can be obtained by ring-closing the polyamic acid of the present invention, and the ring closure can be carried out under heating or in the presence of a dehydrating agent.
  • the temperature for ring closure under heating is not particularly limited, but is preferably 80 to 170 ° C, more preferably 100 to 150 ° C.
  • the polyamic acid of the present invention has a characteristic that it can ring-close at a low temperature as compared with conventionally known polyamic acids.
  • the polyimide of the present invention can be obtained by heating at the above temperature, for example, for 12 to 48 hours.
  • a dehydrating agent for example, an organic acid anhydride such as acetic anhydride or propionic anhydride can be used as the dehydrating agent, as in the conventional ring closure.
  • an organic base such as pyridine, picoline or triethylamine can be used in combination with a dehydrating agent as a catalyst.
  • the temperature and time for ring closure in the presence of a dehydrating agent are the same as described above. After ring closure, the used dehydrating agent and / or catalyst may be removed if necessary.
  • the ring closure is not particularly limited, but can be carried out so that the imidization rate is 70% or more, preferably 80% or more.
  • polyimide has low solvent solubility, and it has been difficult to make a resin composition.
  • the polyimide of the present invention is excellent in solvent solubility, it can be made into a resin composition as described later.
  • Resin composition and molded article The resin composition of the present invention is characterized in that it contains the polyamic acid and / or polyimide of the present invention.
  • a molded article can be produced by removing the solvent from such a resin composition.
  • the above-mentioned resin composition is apply
  • the polyamic acid of the present invention is excellent in low-temperature workability because ring closure is possible even under relatively low temperature conditions.
  • the heating for ring closure may be performed simultaneously with the heating for removing the solvent, or may be performed separately from the heating for removing the solvent.
  • a film can be formed on a substrate simply by placing it at a temperature necessary for the solvent to volatilize after application to the substrate. Therefore, molding at a lower temperature is possible, and there is an advantage that it is not necessary to use a base material and a peripheral member having high heat resistance.
  • the polyamic acid and polyimide of the present invention can be suitably used as a substitute for conventional polyamic acid and polyimide.
  • the use of the resin composition and molded product of the present invention is not particularly limited.
  • an insulating base material for electronic circuit materials an interlayer insulating material for multilayer wiring boards, a protective film for a surface layer of a semiconductor element, a resist material (resist Resin), binder resin of pigment dispersion, paint and ink composition, additives of various heat-resistant resin compositions, matrix resin of fiber reinforced plastic, and the like.
  • the polyamic acid and polyimide of the present invention are preferably used.
  • Synthesis Example 2 Synthesis of Polyimide 1
  • Polyamic acid 1 obtained in Synthesis Synthesis Example 1 was further heated and stirred at a solution internal temperature of 150 ° C. to obtain polyimide 1.
  • the obtained resin had a solid content of 23.9%, a molecular weight of 1,500, and an imidization ratio of 87%.
  • Synthesis Example 3 Synthesis of Polyamic Acid 2
  • a separable flask having a capacity of 300 mL was charged with 240.0 g of N-methyl-2-pyrrolidone, and 33.1 g of 9,9-bis (4-aminophenyl) fluorene was added while stirring.
  • the mixture was gradually added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, 5.2 g of pyromellitic anhydride was gradually added and stirred at 40 ° C. for 7 hours. Further, 2,1.7 g of 1,2,3,6-tetrahydrophthalic anhydride was gradually added and stirred at 40 ° C. for 16 hours to obtain polyamic acid 2.
  • the obtained resin had a solid content of 20.1%, an acid value of 35.3 mgKOH / g, and a molecular weight of 1,400.
  • Synthesis Example 4 Synthesis of Polyimide 2 Polyamic acid 2 obtained in Synthesis Synthesis Example 3 was further heated and stirred at a solution internal temperature of 150 ° C. to obtain polyimide 2.
  • the obtained resin had a solid content of 20.3%, a molecular weight of 1,400, and an imidization ratio of 82%.
  • Synthesis Example 6 Synthesis of Polyimide 3
  • Polyamic acid 3 obtained in Synthesis Synthesis Example 5 was further heated and stirred at a solution internal temperature of 150 ° C. to obtain polyimide 3.
  • the obtained resin had a solid content of 22.0%, a molecular weight of 1,400, and an imidization ratio of 81%.
  • Synthesis Example 7 Synthesis of polyamic acid 4 A separable flask having a capacity of 300 mL was charged with 240.0 g of N-methyl-2-pyrrolidone, and 31.9 g of 9,9-bis (4-aminophenyl) fluorene was stirred. The mixture was gradually added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, 7.1 g of oxydiphthalic dianhydride was gradually added and stirred at 40 ° C. for 7 hours. Further, 20.9 g of 1,2,3,6-tetrahydrophthalic anhydride was gradually added and stirred at 40 ° C. for 16 hours to obtain polyamic acid 4. The obtained resin had a solid content of 20.9%, an acid value of 34.3 mgKOH / g, and a molecular weight of 1,600.
  • Synthesis Example 8 Synthesis of Polyimide 4 Polyamic acid 4 obtained in Synthesis Example 7 was further heated and stirred at a solution internal temperature of 150 ° C. to obtain polyimide 4.
  • the obtained resin had a solid content of 21.5%, a molecular weight of 1,600, and an imidization ratio of 80%.
  • Comparative Synthesis Example 2 Synthesis of Polyimide 5
  • Polyamic acid 5 obtained in Comparative Synthesis Example 1 was further heated and stirred at a solution internal temperature of 150 ° C. to obtain polyimide 5.
  • the obtained resin had a solid content of 23.5%, a molecular weight of 1,100, and an imidation ratio of 51%.
  • solvent solubility Hexane is used as a poor solvent, and polyimide recovered as a solid by reprecipitation is soluble in N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and tetramethylurea (polyimide).
  • the solvent solubility was evaluated in the following two stages by visually confirming 20% by weight and stirring at room temperature. ⁇ : Soluble in solvent (no precipitate is observed)
  • X Insoluble in solvent (precipitate is observed)

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  • Spectroscopy & Molecular Physics (AREA)

Abstract

La présente invention vise à fournir un acide polyamique et un polyimide possédant une excellente aptitude au façonnage à basse température tout en maintenant une résistance élevée à la chaleur. L'acide polyamique est représenté par la formule générale (1) [dans la formule,R1 and R2représentent chacun indépendamment une liaison simple, un groupe alkylène en C1-5, un groupe alcénylène en C2-C5, ou un groupe arylène en C6 -10, R3 et R4représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-5, un groupe alcényle en C2-5, un groupe aryle en C6 -10, ou un atome d'halogène, n représente un nombre entier de 0 à 20, Y représente un résidu à l'exclusion d'un groupe carboxyle d'un acide dicarboxylique ou un groupe anhydride d'acide d'un anhydride dicarboxylique, et Z représente un résidu à l'exclusion d'un groupe carboxyle d'un acide tétracarboxylique ou un groupe anhydride d'acide d'un dianhydride tétracarboxylique].
PCT/JP2015/061557 2014-04-18 2015-04-15 Resine de reserve et son procede de fabrication WO2015159911A1 (fr)

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KR1020167024521A KR20160147712A (ko) 2014-04-18 2015-04-15 레지스트 수지 및 그 제조 방법
JP2016513809A JPWO2015159911A1 (ja) 2014-04-18 2015-04-15 レジスト樹脂及びその製造方法

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WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
WO2020080206A1 (fr) * 2018-10-15 2020-04-23 日産化学株式会社 Composition de résine d'ester de poly(acide amique)

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TWI710585B (zh) * 2017-06-30 2020-11-21 奇美實業股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
WO2019146532A1 (fr) * 2018-01-23 2019-08-01 ナガセケムテックス株式会社 Résine soluble en milieu alcalin contenant un groupe insaturé

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WO2020080206A1 (fr) * 2018-10-15 2020-04-23 日産化学株式会社 Composition de résine d'ester de poly(acide amique)
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JPWO2015159911A1 (ja) 2017-04-13

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