WO2021230199A1 - Résine polyimide, vernis polyimide et film polyimide - Google Patents

Résine polyimide, vernis polyimide et film polyimide Download PDF

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WO2021230199A1
WO2021230199A1 PCT/JP2021/017695 JP2021017695W WO2021230199A1 WO 2021230199 A1 WO2021230199 A1 WO 2021230199A1 JP 2021017695 W JP2021017695 W JP 2021017695W WO 2021230199 A1 WO2021230199 A1 WO 2021230199A1
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structural unit
mol
polyimide
polyimide resin
derived
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PCT/JP2021/017695
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Japanese (ja)
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菜摘 脇田
雅也 甲山
洋平 安孫子
重之 廣瀬
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三菱瓦斯化学株式会社
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Priority to CN202180034072.6A priority Critical patent/CN115551922A/zh
Priority to KR1020227038827A priority patent/KR20230009888A/ko
Priority to JP2022521903A priority patent/JPWO2021230199A1/ja
Publication of WO2021230199A1 publication Critical patent/WO2021230199A1/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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/0017—Casings, cabinets or drawers for electric apparatus with operator interface units
    • 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
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/02—Details
    • H05K5/03—Covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide resin, a polyimide varnish and a polyimide film.
  • Polyimide resins are obtained from, for example, aromatic tetracarboxylic acid anhydrides and aromatic diamines, and are generally excellent in heat resistance, chemical resistance, mechanical properties, and electrical properties due to molecular rigidity, resonance stabilization, and strong chemical bonds. Therefore, it is widely used in the fields of molding materials, composite materials, electrical / electronic parts, optical materials, displays, aerospace, and the like. In the above applications, it is particularly important to have transparency, and studies have been made to enhance the transparency of the polyimide resin.
  • Patent Document 1 discloses a polyimide having TAHMBP or the like as a constituent unit in order to improve transparency, heat resistance, solvent processability, and the like.
  • the problem to be solved by the present invention is a polyimide resin capable of forming a film having both high elasticity and transparency and excellent deformation recovery and elongation while having high elasticity, and both high elasticity and transparency. Further, it is an object of the present invention to provide a polyimide film having excellent deformation recovery and elongation.
  • the polyimide resin having a structural unit derived from two specific types of tetracarboxylic acid dianhydride has both high elasticity and transparency, and has high elasticity and deformation recovery.
  • a film having excellent elongation can be formed, and have reached the present invention.
  • a polyimide resin capable of forming a film having both high elasticity and transparency and excellent deformation recovery and elongation while having high elasticity, a polyimide varnish containing the polyimide resin, and high elasticity and transparency. It is possible to provide a polyimide film that achieves both of the above and is excellent in deformation recovery and elongation.
  • the polyimide resin of the present invention is a polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine.
  • the structural unit A includes a structural unit (A1) derived from the compound represented by the following formula (a1) and a structural unit (A2) derived from the compound represented by the following formula (a2).
  • A1 derived from the compound represented by the following formula (a1)
  • A2 derived from the compound represented by the following formula (a2).
  • the structural unit A contained in the polyimide of the present invention is a structural unit derived from the tetracarboxylic dianhydride in the polyimide resin.
  • the structural unit A includes a structural unit (A1) derived from the compound represented by the formula (a1) and a structural unit (A2) represented by the formula (a2).
  • the compound represented by the formula (a1) is 2,2', 3,3', 5,5'-hexamethyl [1,1'-biphenyl] -4,4'-diyl-bis (1,3-).
  • Dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (TMPBP-TME).
  • TMPBP-TME Dioxo-1,3-dihydro-2-benzofuran-5-carboxylate
  • the constituent unit A includes the constituent unit (A1), the elastic modulus of the obtained polyimide resin is improved.
  • the compound represented by the formula (a2) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • the constituent unit A includes the constituent unit (A2)
  • the transparency can be improved and the elongation can be improved while maintaining the elastic modulus.
  • having a structural unit derived from the above two types of tetracarboxylic dianhydrides achieves both high elasticity and transparency, and excellent deformation recovery and elongation, but an ester group. It is considered to be derived from the rigidity of the alicyclic compound and the transparency of the alicyclic compound.
  • the ratio of the constituent unit (A1) to the constituent unit A is preferably 20 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 80 mol%, still more preferably 50. It is -80 mol%, more preferably 50-70 mol%, still more preferably 55-65 mol%.
  • the ratio of the constituent unit (A2) to the constituent unit A is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 70 mol%, still more preferably 20. It is ⁇ 50 mol%, more preferably 30-50 mol%, still more preferably 35-45 mol%.
  • the ratio of the total of the constituent units (A1) and the constituent units (A2) in the constituent unit A is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 mol% or more.
  • the upper limit of the ratio of the total of the constituent units (A1) and the constituent units (A2) is not particularly limited, and is 100 mol% or less.
  • the constituent unit A may be composed of only the constituent unit (A1) and the constituent unit (A2).
  • the molar ratio [(A1): (A2)] of the structural unit (A1) and the structural unit (A2) in the structural unit A is preferably 20: from the viewpoint of improving elastic modulus, elongation, transparency and deformation recovery. It is 80 to 90:10, more preferably 20:80 to 80:20, still more preferably 30:70 to 80:20, even more preferably 50:50 to 80:20, and even more. It is preferably 50:50 to 70:30, and even more preferably 55:45 to 65:35.
  • the polyimide resin of the present invention is represented by the above formula (a1) as a structural unit other than the above-mentioned structural unit (A1) and the above-mentioned structural unit (A2) in the structural unit A as long as the effect of the present invention is not impaired. It may contain a structural unit derived from a tetracarboxylic dianhydride other than the compound and the compound represented by the above formula (a2).
  • the tetracarboxylic dianhydride other than the compound represented by the above formula (a1) and the compound represented by the above formula (a2) is not particularly limited, but pyromellitic anhydride, 2,3,5,6-.
  • Aromatic tetracarboxylic acid dianhydrides such as toluenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides; 1,2,4,5-cyclopentanetetracarboxylic acid dianhydrides , Bicyclo [2.2.2] octa-7-en-2,3,5,6-tetracarboxylic acid dianhydride, dicyclohexyltetracarboxylic acid dianhydride, or alicyclic tetracarboxylics such as their positional isomers.
  • Acid dianhydride and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-pentanetetracarboxylic acid dianhydride. .. These can be used alone or in combination of two or more.
  • the aromatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic acid dianhydride has one alicyclic ring.
  • the tetracarboxylic acid dianhydride containing the above and containing no aromatic ring is meant, and the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • the structural unit B contained in the polyimide of the present invention is a structural unit derived from diamine.
  • the structural unit derived from the diamine contained in the structural unit B is not limited, but the preferred structural unit will be described below.
  • the structural unit B contained in the polyimide of the present invention preferably contains a structural unit (B1) derived from the compound represented by the following general formula (b1).
  • B1 a structural unit derived from the compound represented by the following general formula (b1).
  • X is a single bond or an oxygen atom.
  • the structural unit (B1) is composed of a group consisting of a structural unit (B11) derived from a compound represented by the following formula (b11) and a structural unit (B12) derived from a compound represented by the following formula (b12). It is preferable to include at least one structural unit selected, and it is more preferable to include a structural unit (B11) derived from the compound represented by the following formula (b11) from the viewpoint of transparency, elastic modulus and colorlessness. Further, from the viewpoint of elongation, it is more preferable to include a structural unit (B12) derived from the compound represented by the following formula (b12).
  • the structural unit (B1) may include only one of the structural unit (B11) and the structural unit (B12), or may include both.
  • the compound represented by the formula (b11) is 2,2'-bis (trifluoromethyl) benzidine (TFMB).
  • the compound represented by the formula (b12) is 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA).
  • the ratio of the constituent unit (B1) to the constituent unit B is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 70 mol% or more. It is more preferably 85 mol% or more. Further, the upper limit of the ratio of the constituent unit (B1) is not particularly limited, and is 100 mol% or less.
  • the structural unit B may include a structural unit (B2) derived from the compound represented by the following formula (b2), and from the viewpoint of improving the elastic modulus, the structural unit B is derived from the compound represented by the following formula (b2). It is preferable to include the unit (B2).
  • the ratio of the constituent unit (B2) to the constituent unit B is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, from the viewpoint of transparency and deformation recovery. It may be 15 mol% or less.
  • the lower limit of the ratio of the structural unit (B2) is not particularly limited and is 0 mol% or more, but is preferably 5 mol% or more from the viewpoint of improving the elastic modulus.
  • the total ratio of the constituent unit (B1) and the constituent unit (B2) in the constituent unit B is preferably 50 mol% or more, and more. It is preferably 70 mol% or more, and more preferably 90 mol% or more.
  • the upper limit of the ratio of the total of the constituent units (B1) and (B2) is not particularly limited, and is 100 mol% or less.
  • the constituent unit B may be composed of only the constituent unit (B1) and the constituent unit (B2).
  • the polyimide resin of the present invention is represented by the above general formula (b1) as a structural unit other than the above-mentioned structural unit (B1) and the above-mentioned structural unit (B2) in the structural unit B as long as the effect of the present invention is not impaired. It may contain a structural unit derived from a diamine other than the compound represented by the above formula (b2) and the compound represented by the above formula (b2).
  • the diamine other than the compound represented by the general formula (b1) and the compound represented by the above formula (b2) is not particularly limited, but is 1,4-phenylenediamine, p-xylylene diamine, 1,5-.
  • the aromatic diamine means a diamine containing one or more aromatic rings
  • the alicyclic diamine means a diamine containing one or more alicyclic rings and does not contain an aromatic ring, and is a fat.
  • the group diamine means a diamine that does not contain an aromatic ring or an alicyclic ring.
  • the number average molecular weight of the polyimide resin of the present invention is preferably 5,000 to 100,000 from the viewpoint of the mechanical strength of the obtained polyimide film.
  • the number average molecular weight of the polyimide resin can be measured by gel filtration chromatography or the like.
  • the polyimide resin of the present invention may be further mixed with various additives as long as the effects of the present invention are not impaired.
  • the additive include antioxidants, light stabilizers, surfactants, flame retardants, plasticizers, polymer compounds other than the polyimide resin, and the like.
  • the polymer compound include polyimides other than the polyimide resin of the present invention, polyesters such as polycarbonate, polystyrene, polyamide, polyamideimide and polyethylene terephthalate, polyethersulfone, polycarboxylic acid, polyacetal, polyphenylene ether, polysulfone, polybutylene, polypropylene and poly. Examples include acrylamide, polyvinyl chloride and the like.
  • the polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing the compound giving the above-mentioned structural unit (A1) and the compound giving the structural unit (A2) with a diamine component.
  • Examples of the compound giving the structural unit (A1) include the compound represented by the formula (a1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a1) and an alkyl ester of the tetracarboxylic acid.
  • the compound giving the structural unit (A1) the compound represented by the formula (a1) (that is, dianhydride) is preferable.
  • the compound giving the structural unit (A2) includes a compound represented by the formula (a2), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a2) and an alkyl ester of the tetracarboxylic acid.
  • the compound represented by the formula (a2) that is, dianhydride
  • the tetracarboxylic acid component contains, preferably 20 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 80 mol%, and even more preferably 50, the compound giving the structural unit (A1). It contains -80 mol%, more preferably 50-70 mol%, still more preferably 55-65 mol%.
  • the tetracarboxylic acid component contains, preferably 10 to 80 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 70 mol%, and even more preferably 20 to the compound giving the structural unit (A2). It contains ⁇ 50 mol%, more preferably 30-50 mol%, still more preferably 35-45 mol%.
  • the total content ratio of the compound giving the structural unit (A1) and the compound giving the structural unit (A2) is preferably 50 mol% or more, more preferably 70 mol% or more, in the total tetracarboxylic acid component. More preferably, it is 90 mol% or more.
  • the upper limit of the total content ratio of the compound giving the structural unit (A1) and the compound giving the structural unit (A2) is not particularly limited and is 100 mol% or less.
  • the tetracarboxylic dian component may consist only of a compound that gives a constituent unit (A1) and a compound that gives a constituent unit (A2).
  • the molar ratio [(A1) :( A2)] of the compound giving the structural unit (A1) and the compound giving the structural unit (A2) in the tetracarboxylic acid component is preferable from the viewpoint of improving the elastic modulus and transparency. It is 20:80 to 90:10, more preferably 20:80 to 80:20, still more preferably 30:70 to 80:20, and even more preferably 50:50 to 80:20. It is even more preferably 50:50 to 70:30, and even more preferably 55:45 to 65:35.
  • the tetracarboxylic acid component may contain a compound other than the compound giving the structural unit (A1) and the compound giving the structural unit (A2), and the compound may include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic type. Examples thereof include tetracarboxylic acid dianhydride and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
  • the compound arbitrarily contained in the tetracarboxylic acid component (that is, a compound other than the compound giving the structural unit (A1) and the structural unit (A2)) may be one kind or two or more kinds.
  • the diamine component is not limited, but preferably contains a compound that gives the above-mentioned structural unit (B1).
  • the compound giving the structural unit (B1) include the compound represented by the formula (b1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • the derivative include diisocyanates corresponding to the diamine represented by the formula (b1).
  • the compound represented by the formula (b1) that is, a diamine is preferable.
  • the diamine component contains, preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol%, still more preferably 70 mol% or more, and more containing the compound giving the constituent unit (B1). More preferably, it contains 85 mol% or more. Further, the upper limit of the ratio of the compound giving the structural unit (B1) is not particularly limited, and is 100 mol% or less.
  • the diamine component may contain a compound that gives a constituent unit (B2), and from the viewpoint of improving the elastic modulus, it is preferable to contain a compound that gives a constituent unit (B2).
  • the compound giving the structural unit (B2) include the compound represented by the formula (b2), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given.
  • the derivative include diisocyanates corresponding to the diamine represented by the formula (b2).
  • the compound represented by the formula (b2) that is, a diamine is preferable.
  • the total content ratio of the compound giving the structural unit (B1) and the compound giving the structural unit (B2) is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 70 mol% or more in the total diamine components. Is 90 mol% or more.
  • the upper limit of the total content ratio of the compound giving the structural unit (B1) and the compound giving the structural unit (B2) is not particularly limited and is 100 mol% or less.
  • the diamine component may consist only of a compound that gives a constituent unit (B1) and a compound that gives a constituent unit (B2).
  • the diamine component may contain a compound that gives a structural unit (B1) and a compound other than the compound that gives a structural unit (B2), and the compound includes the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and modification. Examples thereof include silicone diamines and derivatives thereof (diisocyanates, etc.).
  • the compound arbitrarily contained in the diamine component (that is, a compound other than the compound giving the structural unit (B1) and the compound giving the structural unit (B2)) may be one kind or two or more kinds.
  • the charging amount ratio of the tetracarboxylic acid component and the diamine component is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component. ..
  • an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component.
  • the terminal encapsulant monoamines or dicarboxylic acids are preferable.
  • the amount of the terminal encapsulant to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component.
  • Preferred monoamine terminal encapsulants include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine and 3-ethyl.
  • Benzylamine, aniline, 3-methylaniline, 4-methylaniline and the like can be mentioned. Of these, benzylamine and aniline are more preferable.
  • dicarboxylic acid terminal encapsulant dicarboxylic acids are preferable, and a part thereof may be ring-closed.
  • Preferred dicarboxylic acids include phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid and cyclopentane. Examples thereof include -1,2-dicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid. Of these, phthalic acid and phthalic anhydride are more preferable.
  • the method for reacting the above-mentioned tetracarboxylic acid component and the diamine component is not particularly limited, and a known method can be used.
  • a specific reaction method (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged in a reactor, stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then heated to imidize. Method of carrying out the reaction, (2) The diamine component and the reaction solvent are charged into a reactor and dissolved, then the tetracarboxylic acid component is charged, and if necessary, the mixture is stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then.
  • Examples thereof include a method of carrying out an imidization reaction by raising the temperature to (3) a method of charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor and immediately raising the temperature to carry out the imidization reaction.
  • the reaction solvent used for producing the polyimide resin may be any one that does not inhibit the imidization reaction and can dissolve the produced polyimide resin.
  • an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.
  • aprotonic solvent examples include N, N-dimethylisobutylamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl.
  • Amide solvents such as imidazolidinone and tetramethylurea, lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphintriamide, dimethyl sulfone, Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, ketone solvents such as acetone, cyclohexanone and methylcyclohexane, amine solvents such as picolin and pyridine, ester solvents such as acetic acid (2-methoxy-1-methylethyl), etc. Can be mentioned.
  • phenolic solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
  • ether solvent examples include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
  • the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
  • an amide solvent or a lactone solvent is preferable. Further, the above reaction solvent may be used alone or in combination of two or more.
  • the imidization reaction it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
  • a known imidization catalyst can be used.
  • the imidization catalyst include a base catalyst or an acid catalyst.
  • Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N, N-dimethylaniline. , N, N-diethylaniline and the like, organic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate and the like.
  • the acid catalyst examples include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like. Can be mentioned.
  • the above imidization catalyst may be used alone or in combination of two or more. Of the above, from the viewpoint of handleability, it is preferable to use a base catalyst, more preferably an organic base catalyst, and even more preferably triethylamine.
  • the temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 190 ° C., still more preferably 180 to 190 ° C. from the viewpoint of suppressing the reaction rate and gelation. be.
  • the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
  • the temperature of the imidization reaction when no catalyst is used is preferably 200 to 350 ° C.
  • the polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
  • the organic solvent may be any one that dissolves the polyimide resin, and is not particularly limited, but it is preferable to use the above-mentioned compounds alone or in combination of two or more as the reaction solvent used for producing the polyimide resin.
  • the polyimide varnish of the present invention preferably contains 5 to 60% by mass of the polyimide resin of the present invention, and more preferably 5 to 45% by mass.
  • the viscosity of the polyimide varnish is preferably 0.1 to 200 Pa ⁇ s, more preferably 0.5 to 150 Pa ⁇ s.
  • the polyimide film of the present invention contains the above-mentioned polyimide resin. That is, it has a structural unit A derived from tetracarboxylic acid dianhydride and a structural unit B derived from diamine, and the structural unit A is a structural unit (A1) derived from a compound represented by the following formula (a1). It contains a polyimide resin containing the above-mentioned structural unit (A2) derived from the compound represented by the following formula (a2). By containing such a polyimide resin, the polyimide film of the present invention has both high elasticity and transparency, and is also excellent in deformation recovery.
  • the method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used.
  • a solution containing the polyimide resin of the present invention or a solution containing the solution containing the polyimide resin of the present invention and the various additives described above is applied onto a smooth support such as a glass plate, a metal plate, or plastic.
  • a method of removing a solvent component such as an organic solvent contained in the solution after molding into a film can be mentioned.
  • the solution containing the polyimide resin may be the polyimide resin solution itself obtained by the polymerization method. Further, at least one selected from the compounds exemplified above as a solvent for dissolving the polyimide resin in the polyimide resin solution may be mixed. By adjusting the solid content concentration and viscosity of the solution containing the polyimide resin as described above, the thickness of the polyimide film of the present invention can be easily controlled.
  • a mold release agent may be applied to the surface of the support.
  • the following method is preferable as a method of applying the polyimide resin or a solution containing the polyimide resin composition to the support and then heating to evaporate the solvent component. That is, after evaporating the solvent at a temperature of 120 ° C. or lower to form a self-supporting film, the self-supporting film was peeled off from the support, the end portion of the self-supporting film was fixed, and the solvent component used was used. It is preferable to produce a polyimide film by drying at a temperature of boiling point or higher and 350 ° C. or lower. Further, it is preferable to dry in a nitrogen atmosphere. The pressure in the dry atmosphere may be reduced pressure, normal pressure, or pressurized pressure.
  • the thickness of the polyimide film of the present invention can be appropriately selected depending on the intended use and the like, but is preferably in the range of 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and further preferably 10 to 80 ⁇ m. When the thickness is 1 to 250 ⁇ m, it can be practically used as a self-supporting film. In the present invention, a polyimide film having a total light transmittance of preferably 85% or more, more preferably 88% or more, still more preferably 89% or more at a thickness of 50 ⁇ m can be obtained.
  • a polyimide film having a yellow index (YI value) of preferably 8.0 or less, more preferably 7.5 or less, still more preferably 6.0 or less, still more preferably 4.0 or less can be used. ..
  • the total light transmittance and the YI value of the polyimide film can be specifically measured by the method described in Examples.
  • the polyimide film containing the polyimide resin of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members.
  • the physical characteristics of the polyimide films obtained in the following Examples and Comparative Examples were measured by the methods shown below.
  • Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
  • Tensile elastic modulus (evaluation of elasticity) and tensile strength were measured in accordance with JIS K7127 using a tensile tester "Strograph VG1E” manufactured by Toyo Seiki Co., Ltd.
  • Tensile fracture elongation rate (evaluation of elongation) The tensile elongation at break was determined by a tensile test (measurement of elongation) according to JIS K7127.
  • the test piece used had a width of 10 mm and a thickness of 10 to 70 ⁇ m.
  • Total light transmittance (evaluation of transparency) and YI value were measured in accordance with ASTM E313-05, using a color and turbidity simultaneous measuring device "COH7700" manufactured by Nippon Denshoku Industries Co., Ltd.
  • Example 1 A 300 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean-Stark apparatus with a cooling tube, a thermometer, and a glass end cap, and 2,2'-bis (diamine component) Trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd., compound represented by the formula (b11), hereinafter TFMB) 18.76 g (0.059 mol), ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as an organic solvent.
  • TFMB 2,2'-bis (diamine component) Trifluoromethyl) benzidine
  • a polyimide solution was obtained by collecting the components to be distilled off, maintaining the temperature inside the reaction system at 190 ° C., and refluxing for 2 hours while adjusting the rotation speed according to the increase in viscosity. After that, when the temperature inside the reaction system is cooled to 120 ° C., N, N-dimethylacetamide (manufactured by Mitsubishi Gas Chemical Company, Inc.) is added so as to have a predetermined solid content concentration, and the mixture is further stirred for about 3 hours to homogenize and solidify. A polyimide varnish (A) having a component concentration of 15.0% by mass was obtained.
  • the polyimide varnish (A) is applied onto a glass substrate, held at 60 ° C. for 20 minutes, 80 ° C. for 20 minutes, and 100 ° C. for 30 minutes to volatilize the solvent to provide self-supporting transparent primary.
  • a dried film was obtained, and the film was further fixed to a stainless steel frame and dried at 220 ° C. in an air atmosphere for 20 minutes to remove the solvent to obtain a polyimide film.
  • Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 2 The amount of TFMB was changed to 17.27 g (0.054 mol), and 3,5-diaminobenzoic acid (manufactured by Nippon Junryo Pharmaceutical Co., Ltd., compound represented by the formula (b2), hereinafter 3,5-DABA) was added.
  • Example 1 except that 0.91 g (0.0060 mol) was added and the amount of HPMDA was changed to 5.37 g (0.024 mol) and the amount of TMPBP-TME was changed to 22.23 g (0.036 mol).
  • a polyimide varnish (B) having a solid content concentration of 15.0% by mass was obtained.
  • Example 3 The amount of TFMB was changed to 19.56 g (0.061 mol), the amount of 3,5-DABA was changed to 1.03 g (0.0068 mol), and the amount of HPMDA was changed to 9.13 g (0.041 mol), TMPBP.
  • a polyimide varnish (C) having a solid content concentration of 15.0% by mass was obtained by the same method as in Example 1 except that the amount of TME was changed to 16.79 g (0.027 mol). Using the obtained polyimide varnish (C), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 4 The amount of TFMB was changed to 22.56 g (0.070 mol), 1.19 g (0.0078 mol) of 3,5-DABA was added, and the amount of HPMDA was 14.04 g (0.063 mol), TMPBP-.
  • a polyimide varnish (D) having a solid content concentration of 15.0% by mass was obtained by the same method as in Example 1 except that the amount of TME was changed to 9.68 g (0.016 mol). Using the obtained polyimide varnish (D), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • TFMB is 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (manufactured by ChinaTech Chemical (Taijin) Co., Ltd., compound represented by formula (b12), hereinafter 6FODA) 19.44 g.
  • 6FODA 6FODA
  • Example 6 TFMB was changed to 6FODA 17.79 g (0.053 mol), 3,5-DABA was added 0.90 g (0.0059 mol), HPMDA amount was 5.27 g (0.024 mol), TMPBP-TME.
  • a polyimide varnish (F) having a solid content concentration of 15.0% by mass was obtained by the same method as in Example 1 except that the amount of the above was changed to 21.82 g (0.035 mol). Using the obtained polyimide varnish (F), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • Example 1 By the same method as in Example 1 except that the amount of TFMB was changed to 15.96 g (0.050 mol) and the amount of TMPBP-TME was changed to 30.83 g (0.050 mol) without using HPMDA. A polyimide varnish (G) having a solid content concentration of 15.0% by mass was obtained. Using the obtained polyimide varnish (G), a film was obtained by the same method as in Example 1. Table 1 shows the measurement results and evaluation results of the physical properties.
  • the polyimide films of Examples 1 to 6 have both transparency and elastic modulus, and are also excellent in deformation recovery and elongation.

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Abstract

L'invention concerne une résine polyimide comprenant des unités constitutives A, qui sont dérivées de dianhydrides tétracarboxyliques, et une unité constitutive B, qui est dérivée d'une diamine, les unités constitutives A comprenant une unité constitutive (A1), qui est dérivée de 2,2',3,3',5,5'-hexaméthyl[1,1'-biphényl]-4,4'-diyl bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) et une unité constitutive (A2), qui est dérivée du dianhydride 1,2,4,5-cyclohexanetétracarboxylique.
PCT/JP2021/017695 2020-05-13 2021-05-10 Résine polyimide, vernis polyimide et film polyimide WO2021230199A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009286706A (ja) * 2008-05-27 2009-12-10 Iwatani Industrial Gases Corp 新規な（１ｒ，２ｓ，４ｓ，５ｒ）‐シクロヘキサンテトラカルボン酸二無水物及びその利用
WO2014046180A1 (fr) * 2012-09-19 2014-03-27 本州化学工業株式会社 Polyimide et corps moulé de celui-ci
WO2019211972A1 (fr) * 2018-05-01 2019-11-07 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film polyimide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009286706A (ja) * 2008-05-27 2009-12-10 Iwatani Industrial Gases Corp 新規な（１ｒ，２ｓ，４ｓ，５ｒ）‐シクロヘキサンテトラカルボン酸二無水物及びその利用
WO2014046180A1 (fr) * 2012-09-19 2014-03-27 本州化学工業株式会社 Polyimide et corps moulé de celui-ci
WO2019211972A1 (fr) * 2018-05-01 2019-11-07 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide et film polyimide

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