WO2023276888A1 - Acide polyamique, composition d'acide polyamique, polyimide, film de polyimide, stratifié, procédé de production de stratifié et dispositif électronique - Google Patents

Acide polyamique, composition d'acide polyamique, polyimide, film de polyimide, stratifié, procédé de production de stratifié et dispositif électronique Download PDF

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Publication number
WO2023276888A1
WO2023276888A1 PCT/JP2022/025343 JP2022025343W WO2023276888A1 WO 2023276888 A1 WO2023276888 A1 WO 2023276888A1 JP 2022025343 W JP2022025343 W JP 2022025343W WO 2023276888 A1 WO2023276888 A1 WO 2023276888A1
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polyamic acid
polyimide
weight
polyimide film
organic group
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PCT/JP2022/025343
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English (en)
Japanese (ja)
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博文 中山
友貴 白井
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株式会社カネカ
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Priority to JP2023531905A priority Critical patent/JPWO2023276888A1/ja
Priority to KR1020247003339A priority patent/KR20240027771A/ko
Priority to CN202280046631.XA priority patent/CN117580893A/zh
Publication of WO2023276888A1 publication Critical patent/WO2023276888A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to polyamic acids, polyamic acid compositions, polyimides, polyimide films, laminates, methods for producing laminates, and electronic devices.
  • the present invention further provides electronic device materials using polyimide, thin film transistor (TFT) substrates, flexible display substrates, color filters, printed matter, optical materials, image display devices (more specifically, liquid crystal display devices, organic EL, electronic paper, etc.), 3D displays, solar cells, touch panels, transparent conductive film substrates, and substitute materials for members currently using glass.
  • TFT thin film transistor
  • various electronic elements such as thin film transistors and transparent electrodes, are formed on the substrate, and high-temperature processes are required to form these electronic elements.
  • Polyimide has sufficient heat resistance to adapt to high-temperature processes, and its coefficient of thermal expansion (CTE) is similar to that of glass substrates and electronic devices. be.
  • Aromatic polyimides are generally colored yellowish brown due to intramolecular conjugation and formation of charge transfer (CT) complexes. Transparency is not required, and conventional aromatic polyimides have been used. However, in cases where the light emitted from the display element passes through the substrate, such as in transparent displays, bottom-emission organic EL, and liquid crystal displays, and in smartphones, etc., where full-screen displays (notchless) are required, sensors and When the camera module is arranged on the back surface of the substrate, the substrate is also required to have high optical properties (more specifically, transparency, etc.).
  • CT charge transfer
  • Patent Documents 1 and 2 In order to reduce the coloring of polyimide, a technique for suppressing the formation of a CT complex using an aliphatic monomer (Patent Documents 1 and 2), a technique for increasing transparency using a monomer having a fluorene skeleton (Patent Document 3), and a technique of increasing transparency by using a monomer having a fluorine atom (Patent Document 4).
  • Patent Documents 1 and 2 have high transparency and a low CTE, but because they have an aliphatic structure, they have a low thermal decomposition temperature and are difficult to apply to high-temperature processes when forming electronic elements.
  • the polyimide described in Patent Document 3 has high transparency and high heat resistance due to the introduction of a fluorene skeleton.
  • the polyimide described in Patent Document 3 has a high coefficient of thermal expansion (CTE). internal stress tends to increase. For this reason, when a laminate is formed using the polyimide described in Patent Document 3, the laminate is likely to warp, which may make it difficult to apply to electronic devices.
  • CTE coefficient of thermal expansion
  • Patent Document 4 also reduces the internal stress between the support and the polyimide film (hereinafter sometimes simply referred to as "internal stress"), while the polyimide having excellent transparency and heat resistance is difficult to obtain.
  • the present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a polyimide having excellent transparency and heat resistance while reducing internal stress, and a polyamic acid as a precursor thereof. Another object of the present invention is to provide a product or member that is produced using the polyimide and polyamic acid and that requires heat resistance and transparency. In particular, it is an object of the present invention to provide a product or member in which the polyimide film of the present invention is formed on the surface of an inorganic material such as glass, metal, metal oxide, or single crystal silicon.
  • the present invention includes the following aspects.
  • R 1 and R 2 each independently represent a hydrogen atom, a monovalent aliphatic group or a monovalent aromatic group, and X 1 represents a divalent organic group.
  • X 1 is a divalent organic group represented by the following chemical formula (2-1) and a divalent organic group represented by the following general formula (2-2) Polyamic acid according to the above [1] or [2], which is one or more selected from the group consisting of.
  • Y 1 is a divalent organic group represented by the following chemical formula (3-1), a divalent organic group represented by the following chemical formula (3-2), a divalent organic group represented by (3-3), a divalent organic group represented by the following chemical formula (3-4), a divalent organic group represented by the following chemical formula (3-5), and It is one or more selected from the group consisting of divalent organic groups represented by the following chemical formula (3-6).
  • R 3 and R 4 each independently represent a hydrogen atom, a monovalent aliphatic group or a monovalent aromatic group
  • X 2 represents a divalent organic group
  • Y 2 is a tetravalent organic group represented by the following chemical formula (5-1), a tetravalent organic group represented by the following chemical formula (5-2), or a tetravalent organic group represented by the following chemical formula (5-3). It is one or more selected from the group consisting of a valent organic group and a tetravalent organic group represented by the following chemical formula (5-4).
  • a polyimide which is an imidized polyamic acid according to any one of [1] to [5].
  • the support is a glass substrate, The laminate according to [14], wherein the internal stress between the polyimide film and the glass substrate is 40 MPa or less.
  • a method for producing a laminate having a support and a polyimide film By applying the polyamic acid composition according to any one of [6] to [8] on a support, a coating film containing the polyamic acid is formed, and the coating film is heated to obtain the polyamide A method for producing a laminate by imidating an acid.
  • the polyimide produced using the polyamic acid according to the present invention has excellent transparency and heat resistance while reducing internal stress. Therefore, the polyimide produced using the polyamic acid according to the present invention is suitable as a material for electronic devices that require transparency and heat resistance and are produced through high-temperature processes.
  • a “structural unit” refers to a repeating unit that constitutes a polymer.
  • a “polyamic acid” is a polymer containing a structural unit represented by the following general formula (6) (hereinafter sometimes referred to as “structural unit (6)").
  • structural unit (6) a structural unit represented by the following general formula (6)
  • polyamic acid esters polyamic acid alkyl esters, polyamic acid aryl esters, etc.
  • R 5 and R 6 each independently represent a hydrogen atom, a monovalent aliphatic group or a monovalent aromatic group
  • a 1 is, for example, a tetracarboxylic dianhydride residue group (tetravalent organic group derived from tetracarboxylic dianhydride)
  • A2 represents, for example, a diamine residue (divalent organic group derived from diamine).
  • the content of the structural unit (6) with respect to all structural units constituting the polyamic acid is, for example, 50 mol% or more and 100 mol% or less, preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol%. 100 mol % or more, more preferably 80 mol % or more and 100 mol % or less, even more preferably 90 mol % or more and 100 mol % or less, and may be 100 mol %.
  • 1% weight loss temperature is the measurement temperature when the weight of polyimide at a measurement temperature of 150°C is taken as the reference (100% by weight), and the weight is reduced by 1% by weight with respect to the reference weight.
  • the method for measuring the 1% weight loss temperature is the same method as in Examples described later or a method based thereon.
  • m/z is a measurement that can be read from the horizontal axis of the mass spectrum, which is the result of mass spectrometry, and is "a dimensionless quantity obtained by dividing the mass of an ion by the unified atomic mass unit (Dalton). is further divided by the absolute value of the ion charge number.
  • system may be added after the name of the compound to generically refer to the compound and its derivatives.
  • polymer name is expressed by adding "system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative.
  • a tetracarboxylic dianhydride may be described as an "acid dianhydride”.
  • the components, functional groups, and the like exemplified in this specification may be used alone or in combination of two or more.
  • the polyamic acid according to the present embodiment includes a structural unit represented by the following general formula (1) (hereinafter sometimes referred to as "structural unit (1)”), and has a fluorine atom content of 5% by weight or less. is.
  • R 1 and R 2 each independently represent a hydrogen atom, a monovalent aliphatic group or a monovalent aromatic group, and X 1 represents a divalent organic group.
  • R 1 and R 2 each independently preferably represent a hydrogen atom, a methyl group or an ethyl group, and more preferably both R 1 and R 2 represent a hydrogen atom.
  • structural unit (1) a structural unit in which R 1 and R 2 in general formula (1) each represent a hydrogen atom is referred to as structural unit (1).
  • Structural unit (1) is spiro[11H-diflo[3,4-b:3′,4′-i]xanthene-11,9′-[9H]fluorene]-1,3,7,9-tetrone ( hereinafter, it may be referred to as “SFDA”). That is, structural unit ( 1 ) has an SFDA residue as A1 in general formula (6) described above.
  • the polyamic acid according to the present embodiment contains the structural unit (1) and has a fluorine atom content of 5% by weight or less
  • the polyimide produced using the polyamic acid according to the present embodiment has internal stress. Excellent transparency and heat resistance while reducing The reason is presumed as follows.
  • SFDA has a rigid structure derived from the xanthene skeleton, it is suitable as a raw material (monomer) for polyimide with a high glass transition temperature (excellent in heat resistance), and is also a raw material (monomer) for polyimide with a low CTE. ) is suitable as In addition, SFDA is suitable as a raw material (monomer) for highly transparent polyimide due to its fluorene skeleton.
  • the polyamic acid containing the structural unit (1) has a xanthene skeleton in the main chain and a fluorene skeleton in the side chain. Therefore, the polyimide film produced using the polyamic acid containing the structural unit (1) Shows low retardation.
  • the polyamic acid according to the present embodiment has an SFDA residue that contributes to a low CTE and has a fluorine atom content of 5% by weight or less, so that a polyimide film is formed on the support to form a laminate It is possible to reduce the internal stress generated when obtaining Therefore, the polyimide produced using the polyamic acid according to the present embodiment can have reduced internal stress.
  • the polyamic acid according to the present embodiment has an SFDA residue that contributes to transparency and heat resistance
  • the polyimide produced using the polyamic acid according to the present embodiment has excellent transparency and heat resistance.
  • the fluorine atom content of the polyamic acid (hereinafter sometimes referred to as "polyamic acid (1)") according to the present embodiment is preferably less than 1% by weight. , more preferably less than 0.5% by weight, more preferably less than 0.1% by weight, and substantially 0% by weight (polyamic acid (1) contains residues derived from fluorine-containing monomers not included) is particularly preferred.
  • the fluorine atom content (unit: % by weight) is the ratio of the fluorine atom weight to the total weight of the polyamic acid.
  • Polyamic acid is a polyadduct of diamine and tetracarboxylic dianhydride, and the total weight of diamine and tetracarboxylic dianhydride before polymerization is equal to the weight of polyamic acid after polymerization. That is, the fluorine atom content of the polyamic acid is the value obtained by dividing the "total weight of fluorine atoms contained in the monomers for forming the polyamic acid" by the "total weight of the monomers for forming the polyamic acid". obtained by multiplying Therefore, the fluorine atom content of polyamic acid can be calculated based on the following formula.
  • ni is the amount (unit: mol) of diamine component i
  • nj is the amount (unit: mol) of tetracarboxylic dianhydride j
  • M i is the molecular weight of diamine component i
  • M j is the molecular weight of tetracarboxylic dianhydride j
  • F i is the number of fluorine atoms contained in one molecule of diamine component i
  • F j is the number of fluorine atoms contained in one molecule of tetracarboxylic dianhydride j.
  • 19.00 is the atomic weight of fluorine.
  • Structural unit (1) has an SFDA residue and a diamine residue (a divalent organic group represented by X 1 in general formula (1)).
  • diamines containing no fluorine atoms are preferred as the diamines that give X 1 in the general formula (1).
  • diamines containing no fluorine atom examples include p-phenylenediamine (hereinafter sometimes referred to as "PDA”) and 4-aminophenyl-4-aminobenzoate (hereinafter referred to as "4-BAAB").
  • PDA p-phenylenediamine
  • 4-BAAB 4-aminophenyl-4-aminobenzoate
  • DABA 4,4′-diaminobenzanilide
  • BABB 1,4-bis(4-aminobenzoyloxy)benzene
  • PBAB N,N'-(1,4-phenylene)bis(4-aminobenzamide)
  • BATP bis(4-aminophenyl) terephthalate
  • DATA N,N'-di(4-aminophenyl)terephthalamide
  • PAM-E 1,4-diaminocyclohexane, m-phenylenediamine, 9,9-bis(4-aminophenyl)fluorene, 4,4'-oxydianiline , 3,4
  • X 1 in general formula (1) is a PDA residue, a 4-BAAB residue, a DABA residue, a BABB residue. , PBAB residues, BATP residues and DATA residues.
  • a PDA residue is a divalent organic group represented by the following chemical formula (2-1).
  • 4-BAAB residue is a divalent organic group represented by the following general formula (2-2), and represented by the following chemical formula (3-1) as Y 1 in the general formula (2-2) It has a divalent organic group that DABA residue is a divalent organic group represented by the following general formula (2-2), and 2 represented by the following chemical formula (3-2) as Y 1 in general formula (2-2) have a valent organic group.
  • BABB residue is a divalent organic group represented by the following general formula (2-2), and 2 represented by the following chemical formula (3-3) as Y 1 in general formula (2-2) have a valent organic group.
  • the PBAB residue is a divalent organic group represented by the following general formula (2-2), and 2 represented by the following chemical formula (3-4) as Y 1 in the general formula (2-2) have a valent organic group.
  • BATP residue is a divalent organic group represented by the following general formula (2-2), and 2 represented by the following chemical formula (3-5) as Y 1 in the general formula (2-2) have a valent organic group.
  • DATA residue is a divalent organic group represented by the following general formula (2-2), and 2 represented by the following chemical formula (3-6) as Y 1 in general formula (2-2) have a valent organic group.
  • X 1 in general formula (1) is preferably a PDA residue.
  • X 1 in the general formula (1) is preferably one or more selected from the group consisting of 4-BAAB residues, BABB residues and BATP residues, 4-BAAB residues are more preferred.
  • X 1 in general formula (1) is preferably one or more selected from the group consisting of DABA residues, PBAB residues and DATA residues. A residue is more preferred.
  • PDA residues In order to obtain a polyimide that is more excellent in transparency and heat resistance while further reducing internal stress, PDA residues, 4-BAAB residues, DABA residues,
  • the content of one or more residues selected from the group consisting of BABB residues, PBAB residues, BATP residues and DATA residues is 30 mol% or more. is preferably 40 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, 70 mol% or more, 80 mol% or more, or 90 mol % or more, or 100 mol %.
  • the polyamic acid (1) preferably contains a PAM-E residue. More preferably, the content of PAM-E residues relative to diamine residues is 0.01 mol % or more and 1 mol % or less.
  • an acid dianhydride other than SFDA may be used as a monomer.
  • acid dianhydrides other than SFDA are preferably acid dianhydrides containing no fluorine atoms.
  • Acid dianhydrides containing no fluorine atom include, for example, pyromellitic dianhydride (hereinafter sometimes referred to as "PMDA") and 3,3',4,4'-biphenyltetracarboxylic dianhydride.
  • PMDA pyromellitic dianhydride
  • 3,3',4,4'-biphenyltetracarboxylic dianhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride.
  • BPDA 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • BPAF 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • ODPA 4,4 '-Oxydiphthalic anhydride
  • 2,3,6,7-naphthalenetetracarboxylic dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, dicyclohexyl-3,3′,4,4′- Tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and derivatives thereof, which may be used alone or Two or more types may be used alone
  • polyamic acid (1) contains, as acid dianhydride residues other than SFDA residues, PMDA residues, BPDA residues, It preferably contains one or more selected from the group consisting of BPAF residues and ODPA residues.
  • the polyamic acid (1) is a structural unit represented by the following general formula (4) (hereinafter, “structural unit ( 4)”) is preferably further included.
  • R 3 and R 4 each independently represent a hydrogen atom, a monovalent aliphatic group or a monovalent aromatic group
  • X 2 represents a divalent organic group
  • Y 2 is a tetravalent organic group represented by the following chemical formula (5-1), a tetravalent organic group represented by the following chemical formula (5-2), a tetravalent organic group represented by the following chemical formula (5-3) and a tetravalent organic group represented by the following chemical formula (5-4).
  • a PMDA residue is a tetravalent organic group represented by the chemical formula (5-1).
  • a BPDA residue is a tetravalent organic group represented by the chemical formula (5-2).
  • a BPAF residue is a tetravalent organic group represented by the chemical formula (5-3).
  • the ODPA residue is a tetravalent organic group represented by chemical formula (5-4).
  • preferred groups for R 3 , R 4 and X 2 are, for example, the same as the preferred groups for R 1 , R 2 and X 1 in general formula (1). .
  • the content of SFDA residues with respect to all acid dianhydride residues constituting polyamic acid (1) is 5 mol% or more. is preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, 30 mol% or more, 40 mol% or more, or It may be 50 mol % or more, or 100 mol %.
  • PMDA residue, BPDA residue, BPAF residue for all acid dianhydride residues constituting polyamic acid (1) and the content of one or more residues selected from the group consisting of ODPA residues (if two or more are included, the total content) is preferably 5 mol% or more, and 10 mol% or more. is more preferably 20 mol% or more, even more preferably 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more or 80 mol% or more.
  • the content of one or more residues selected from the group consisting of residues and ODPA residues is preferably 95 mol% or less, and 90 mol% or less. It is more preferable to have
  • the polyamic acid (1) may contain a BPDA residue as an acid dianhydride residue other than the SFDA residue.
  • a BPDA residue as an acid dianhydride residue other than the SFDA residue.
  • the substance amount ratio of the SFDA residue to the BPDA residue is preferably 10/90 or more and 50/50 or less, more preferably 10/90 or more and 40/60 or less, and further preferably 10/90 or more and 35/65 or less. It is more preferably 10/90 or more and 30/70 or less.
  • the polyamic acid (1) may contain only the structural unit (1) as a structural unit, or may contain only the structural unit (1) and the structural unit (4), and the structural unit (1) and the structural A structural unit (another structural unit) other than the unit (4) may be included.
  • the content of the structural unit (1) with respect to the total structural units constituting the polyamic acid (1) is 5 mol% or more. is preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% % or more, or 100 mol %.
  • the total content of structural unit (1) and structural unit (4) is preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and 80 mol% or more. It is more preferably 100 mol % or less, even more preferably 90 mol % or more and 100 mol % or less, and may be 100 mol %.
  • the polyamic acid (1) preferably satisfies the following condition 1, more preferably satisfies the following condition 2. It is more preferable to satisfy condition 3.
  • Condition 1 Polyamic acid (1) contains a BPDA residue as an acid dianhydride residue other than an SFDA residue, and does not contain a residue derived from a fluorine-containing monomer.
  • Condition 2 satisfying condition 1 above, and polyamic acid (1) is selected from the group consisting of a PDA residue, a 4-BAAB residue, a DABA residue, a BABB residue, a PBAB residue, a BATP residue and a DATA residue It contains one or more selected diamine residues.
  • Condition 3 Satisfies Condition 2 above, and the substance amount ratio of SFDA residues to BPDA residues (SFDA residues/BPDA residues) is 10/90 or more and 35/65 or less.
  • Polyamic acid (1) can be synthesized by a known general method, and can be obtained, for example, by reacting a diamine and a tetracarboxylic dianhydride in an organic solvent.
  • An example of a specific method for synthesizing polyamic acid (1) will be described.
  • a diamine solution is prepared by dissolving or dispersing a diamine in an organic solvent in an inert gas atmosphere such as argon or nitrogen.
  • the tetracarboxylic dianhydride is added to the diamine solution after dissolving it in an organic solvent or dispersing it in a slurry state, or in a solid state.
  • the substance amount of the diamine when using multiple types of diamines, the substance amount of each diamine
  • the tetracarboxylic dianhydride By adjusting the amount of substance (when using multiple types of tetracarboxylic dianhydrides, the amount of each tetracarboxylic dianhydride), the desired polyamic acid (1) (diamine and tetracarboxylic acid dianhydride polymer with anhydride) can be obtained.
  • the molar fraction of each residue in polyamic acid (1) matches, for example, the molar fraction of each monomer (diamine and tetracarboxylic dianhydride) used in synthesizing polyamic acid (1).
  • Polyamic acid (1) containing multiple types of tetracarboxylic dianhydride residues and multiple types of diamine residues can also be obtained by blending two types of polyamic acid.
  • the temperature conditions for the reaction between the diamine and the tetracarboxylic dianhydride, that is, the synthesis reaction of the polyamic acid (1) are not particularly limited, but are, for example, in the range of 20°C or higher and 150°C or lower.
  • the reaction time for the synthetic reaction of polyamic acid (1) is, for example, in the range of 10 minutes or more and 30 hours or less.
  • the organic solvent used for synthesizing polyamic acid (1) is preferably a solvent capable of dissolving the tetracarboxylic dianhydride and diamine used, and more preferably a solvent capable of dissolving polyamic acid (1) to be produced.
  • organic solvents used for synthesizing polyamic acid (1) include urea-based solvents such as tetramethylurea and N,N-dimethylethylurea; sulfoxide-based solvents such as dimethylsulfoxide; diphenylsulfone and tetramethylsulfone.
  • Sulfone-based solvents such as; N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 3-methoxy-N , N-dimethylpropanamide (MPA), hexamethylphosphoric triamide and other amide solvents; ⁇ -butyrolactone and other ester solvents; chloroform, methylene chloride and other halogenated alkyl solvents; benzene, toluene and other aromatic carbonization Hydrogen-based solvents; phenolic solvents such as phenol and cresol; ketone-based solvents such as cyclopentanone; Ether-based solvents such as cresol methyl ether are included.
  • DMAC N,N-dimethylacetamide
  • DMF N,N-dimethylformamide
  • NMP N,N-diethylacetamide
  • NMP N-methyl-2-pyr
  • the organic solvent used in the synthetic reaction of the polyamic acid (1) consists of amide solvents, ketone solvents, ester solvents and ether solvents.
  • amide solvents more specifically, DMF, DMAC, NMP, MPA, etc.
  • the synthetic reaction of polyamic acid (1) is preferably carried out in an inert gas atmosphere such as argon or nitrogen.
  • the weight average molecular weight of the polyamic acid (1) is preferably in the range of 10,000 or more and 1,000,000 or less, and more preferably in the range of 20,000 or more and 500,000 or less, depending on the application. More preferably, it is in the range of 30,000 or more and 200,000 or less. If the weight-average molecular weight is 10,000 or more, polyamic acid (1) or polyimide obtained using polyamic acid (1) can be easily formed into a coating film or a polyimide film (film). On the other hand, when the weight-average molecular weight is 1,000,000 or less, it exhibits sufficient solubility in a solvent, so a coating film or polyimide film having a smooth surface and a uniform thickness using a polyamic acid composition described later is obtained.
  • the weight average molecular weight used here means a polyethylene oxide equivalent value measured using gel permeation chromatography (GPC).
  • a method for controlling the molecular weight of the polyamic acid (1) a method of using either an acid dianhydride or a diamine in excess, a monofunctional acid anhydride such as phthalic anhydride or aniline, or an amine A method of quenching the reaction by reacting is included.
  • a polyimide film having sufficient strength can be obtained if the molar ratio of these charged is between 0.95 and 1.05.
  • the molar ratio of the charge is the ratio of the total amount of diamines used in the synthesis of polyamic acid (1) to the total amount of acid dianhydrides used in the synthesis of polyamic acid (1) (total amount of diamines amount/total substance amount of acid dianhydride). Further, by terminal-capping with phthalic anhydride, maleic anhydride, aniline, or the like, coloring of the polyimide obtained using the polyamic acid (1) can be further reduced.
  • the polyamic acid composition according to the present embodiment contains polyamic acid (1) and an organic solvent.
  • the organic solvent contained in the polyamic acid composition include the organic solvents exemplified as the organic solvent that can be used in the synthesis reaction of the polyamic acid (1), and include amide solvents, ketone solvents, ester solvents and One or more solvents selected from the group consisting of ether solvents are preferable, and amide solvents (more specifically, DMF, DMAC, NMP, MPA, etc.) are more preferable.
  • the reaction solution solution after reaction itself may be used as the polyamic acid composition according to the present embodiment.
  • the solid polyamic acid (1) obtained by removing the solvent from the reaction solution may be dissolved in an organic solvent to prepare the polyamic acid composition according to the present embodiment.
  • the content of polyamic acid (1) in the polyamic acid composition according to the present embodiment is not particularly limited, but is, for example, 1% by weight or more and 80% by weight or less based on the total amount of the polyamic acid composition.
  • the polyamic acid composition according to the present embodiment may contain an imidization accelerator and/or a dehydration catalyst in order to shorten the heating time and develop properties.
  • a tertiary amine can be used as the imidization accelerator.
  • a heterocyclic tertiary amine is preferred as the tertiary amine.
  • Preferable specific examples of heterocyclic tertiary amines include pyridine, picoline, quinoline, isoquinoline and imidazoles.
  • Preferred specific examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
  • the amount of the imidization accelerator is preferably 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamic acid (1). It is more preferably 0.5 parts by weight or more and 5 parts by weight or less.
  • the amount of the dehydration catalyst is preferably 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamic acid (1). It is more preferably 0.5 parts by weight or more and 5 parts by weight or less.
  • imidazoles are preferable.
  • imidazoles refer to compounds having a 1,3-diazole ring (1,3-diazole ring structure).
  • the imidazoles added to the polyamic acid composition according to the present embodiment are not particularly limited, but examples include 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole and the like.
  • 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole are preferred, and 1,2-dimethylimidazole and 1-benzyl-2-methylimidazole are more preferred. .
  • the content of the imidazole is preferably 0.005 mol or more and 0.1 mol or less, and 0.01 mol or more and 0.08 mol or less, relative to 1 mol of the amide group of the polyamic acid (1). is more preferably 0.015 mol or more and 0.050 mol or less.
  • a polymerization solvent such as NMP forms a complex by hydrogen bonding with the carboxy group of polyamic acid (1).
  • amide group of polyamic acid (1) refers to an amide group produced by a polymerization reaction of diamine and tetracarboxylic dianhydride.
  • the method of mixing polyamic acid (1) and imidazoles is not particularly limited. From the viewpoint of ease of controlling the molecular weight of polyamic acid (1), it is preferable to add imidazoles to polyamic acid (1) after polymerization. At this time, the imidazole may be added as it is to the polyamic acid (1), or the imidazole may be dissolved in a solvent in advance and this solution may be added to the polyamic acid (1). Not restricted.
  • the polyamic acid composition according to the present embodiment may be prepared by adding imidazoles to a solution containing polyamic acid (1) after polymerization (solution after reaction).
  • additives may be added as additives to the polyamic acid composition according to the present embodiment.
  • additives include plasticizers, antioxidants, dyes, surfactants, leveling agents, silicones, fine particles, and sensitizers.
  • the fine particles include organic fine particles made of polystyrene, polytetrafluoroethylene, etc., inorganic fine particles made of colloidal silica, carbon, layered silicate, etc. They may have a porous structure or a hollow structure.
  • the function and form of the fine particles are not particularly limited, and may be, for example, pigments, fillers, or fibrous particles.
  • the plasticizer is preferably a compound that dissolves in the organic solvent used for polymerization of the polyamic acid (1) and that exists as a liquid during imidization. Moreover, the plasticizer preferably does not volatilize at low temperatures in order to impart sufficient molecular mobility to the polyamic acid (1) during imidization. Therefore, the boiling point of the plasticizer is preferably 50°C or higher, more preferably 100°C or higher, and even more preferably 150°C or higher. Moreover, the plasticizer preferably does not have a decomposition temperature below the boiling point in order to impart sufficient molecular mobility to the polyamic acid (1) during imidization.
  • the amount of the plasticizer is 0.001 part by weight or more with respect to 100 parts by weight of the polyamic acid (1), from the viewpoint of imparting sufficient molecular mobility to the polyamic acid (1) and avoiding decomposition of the plasticizer itself. It is preferably 20 parts by weight or less, more preferably 0.01 parts by weight or more and 15 parts by weight or less, still more preferably 0.05 parts by weight or more and 10 parts by weight or less, and 0.05 parts by weight or more. Even more preferably, it is 5 parts by weight or less.
  • the plasticizer not only improves molecular motion when polyamic acid (1) undergoes dehydration ring closure to polyimide, but can also add functions such as adjustment of the glass transition temperature and flame retardancy.
  • the plasticizer for example, one or more of known plasticizers can be appropriately selected and used.
  • the plasticizer is preferably one or more selected from the group consisting of phosphorus-containing compounds, polyalkylene glycols and aliphatic dibasic acid esters.
  • Preferred examples of phosphorus-containing compounds include phosphoric acid compounds, phosphorous acid compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine compounds, phosphine oxide compounds, phosphorane compounds, phosphazene compounds, and the like.
  • the phosphorus-containing compound may be an ester of the compounds listed above or a condensate thereof, may contain a cyclic structure, or may form a salt with an amine or the like. Further, some of these phosphorus-containing compounds have a tautomeric relationship, such as a phosphorous acid-based compound and a phosphonic acid-based compound, but they may exist in either state.
  • phosphoric acid compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl ) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyl oxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-meth
  • phosphorous acid compounds include triphenylphosphite, trisnonylphenylphosphite, tricresylphosphite, triethylphosphite, triisobutylphosphite, tris(2-ethylhexyl)phosphite and tridecylphosphite.
  • trilauryl phosphite tris (tridecyl) phosphite, diphenyl phosphite, diethyl phosphite, dibutyl phosphite, dimethyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphites, trilauryl trithiophosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, Bis (decyl) pentaerythritol diphosphite, bis (tridecy
  • condensates examples include condensed phosphate esters.
  • specific examples of the condensed phosphate include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate, hydroquinone poly(2,6-xylyl) phosphate, and the like.
  • Commercially available condensed phosphate esters include, for example, “CR-733S” manufactured by Daihachi Chemical Industry Co., Ltd., “CR-741” manufactured by Daihachi Chemical Industry Co., Ltd., and “FP-600” manufactured by ADEKA Corporation.
  • phosphazene-based compounds include phenoxycyclophosphazene (“FP-110” manufactured by Fushimi Pharmaceutical Co., Ltd.), cyclic cyanophenoxyphosphazene (“FP-300” manufactured by Fushimi Pharmaceutical Co., Ltd.), and the like.
  • Polyalkylene glycol includes polypropylene glycol, polyethylene glycol, and the like.
  • aliphatic dibasic acid esters include dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis[2-(2-butoxyethoxy)ethyl]adipate, bis(2- ethylhexyl)azelate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, diethyl succinate and the like.
  • the plasticizer may be a low-molecular-weight organic compound or a thermoplastic resin as long as it exhibits a plasticizing effect.
  • the low-molecular-weight organic compounds include organic compounds having a molecular weight of about 1,000 or less, such as phthalimide compounds such as phthalimide, N-phenylphthalimide, N-glycidylphthalimide, N-hydroxyphthalimide, and cyclohexylthiophthalimide; Examples include maleimide compounds such as N,Np-phenylenebismaleimide and 2,2'-(ethylenedioxy)bis(ethylmaleimide).
  • the thermoplastic resin include polyimide and polyamide having an asymmetric structure.
  • antioxidants examples include phenolic compounds, and phenolic compounds that dissolve in the organic solvent used for polymerization of the polyamic acid (1) and that exist as a liquid during imidization are preferred. From the viewpoint of suppressing the coloring of the polyimide film, it is desirable that it remains during imidization. It is more preferable that it is above. Phenolic compounds that do not have a decomposition temperature below the boiling point are preferred.
  • phenolic compound examples include hindered type, semi-hindered type, less hindered type, etc. Specific examples include dibutylhydroxytoluene, 1,3,5-tris(3,5-di-t-butyl -4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl acrylate, and the like. mentioned.
  • Phenolic compounds mainly capture peroxy radicals, convert them to hydroperoxides, and function as primary antioxidants that suppress autoxidation of polymers, so they have the function of suppressing coloration due to oxidation of polymers. Furthermore, by combining a phenolic compound with a phosphite or the like that functions as a secondary antioxidant that converts hydroperoxide into a stable alcohol compound, coloration due to oxidation of polyimide can be further suppressed. For example, the coloring of the polyimide can be effectively suppressed by using the phosphite ester in the range of equivalent weight or more and 10 equivalents or less with respect to the phenolic compound.
  • the amount of the phenolic compound is preferably 0.001 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamic acid (1). It is more preferably from 0.02 part by weight to 5 parts by weight, and even more preferably from 0.02 part by weight to 1 part by weight.
  • the phenolic compound may be dissolved in an organic solvent before polymerization of polyamic acid (1), or may be added to the polyamic acid solution after polymerization.
  • nanosilica particles may be used as the additive, and the polyamic acid (1) and the nanosilica particles may be combined.
  • the average primary particle size of the nanosilica particles is preferably 200 nm or less, more preferably 100 nm or less, even more preferably 50 nm or less, and 30 nm or less.
  • the average primary particle size of the nanosilica particles is preferably 5 nm or more, more preferably 10 nm or more.
  • a known method can be used, for example, a method using an organosilica sol in which nanosilica particles are dispersed in an organic solvent.
  • a method of combining polyamic acid (1) and nanosilica particles using organosilica sol after synthesizing polyamic acid (1), a method of mixing synthesized polyamic acid (1) and organosilica sol is used.
  • the nanosilica particles can be surface-treated with a surface treatment agent in order to enhance the interaction with the polyamic acid (1).
  • a surface treatment agent a known agent such as a silane coupling agent can be used.
  • a silane coupling agent an alkoxysilane compound having an amino group, a glycidyl group, or the like as a functional group is widely known, and can be appropriately selected.
  • the silane coupling agent is preferably an amino group-containing alkoxysilane.
  • amino group-containing alkoxysilanes examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethyl ) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 2-aminophenyltrimethoxysilane and 3-aminophenyltrimethoxysilane.
  • Silanes are preferably used.
  • a method of stirring a mixture obtained by adding a silane coupling agent to a dispersion (organosilica sol) at an ambient temperature of 20° C. or higher and 80° C. or lower may be mentioned.
  • the stirring time at this time is, for example, 1 hour or more and 10 hours or less.
  • a catalyst or the like that promotes the reaction may be added.
  • a nanosilica-polyamic acid composite obtained by combining polyamic acid (1) and nanosilica particles contains 1 part by weight or more and 30 parts by weight or less of nanosilica particles with respect to 100 parts by weight of polyamic acid (1). and more preferably in the range of 1 part by weight or more and 20 parts by weight or less.
  • the content of the nanosilica particles is 1 part by weight or more, the heat resistance of the nanosilica particle-containing polyimide can be improved and the internal stress can be sufficiently reduced. Adverse effects on the mechanical properties of polyimide containing nanosilica particles can be suppressed.
  • the polyamic acid composition according to the present embodiment can contain a silane coupling agent in order to exhibit appropriate adhesion to the support.
  • a silane coupling agent known ones can be used without particular limitation, but compounds containing an amino group are particularly preferred from the viewpoint of reactivity with polyamic acid (1).
  • the mixing ratio of the silane coupling agent to 100 parts by weight of polyamic acid (1) is preferably 0.01 parts by weight or more and 0.50 parts by weight or less, and 0.01 parts by weight or more and 0.10 parts by weight or less. more preferably 0.01 parts by weight or more and 0.05 parts by weight or less.
  • the polyimide according to this embodiment is an imidized product of polyamic acid (1) described above.
  • the polyimide according to this embodiment can be obtained by a known method, and the production method is not particularly limited. An example of a method for imidating the polyamic acid (1) to obtain the polyimide according to the present embodiment will be described below. Imidation is carried out by dehydration and ring closure of polyamic acid (1). This dehydration ring closure can be carried out by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method.
  • imidization of polyamic acid (1) to polyimide can take any ratio of 1% or more and 100% or less. That is, a partially imidized polyamic acid (1) may be synthesized.
  • the dehydration ring closure of the polyamic acid (1) may be performed by heating the polyamic acid (1).
  • the method of heating the polyamic acid (1) is not particularly limited, but for example, the polyamic acid composition according to the present embodiment is applied onto a support such as a glass substrate, a metal plate, or a PET film (polyethylene terephthalate film). After that, the polyamic acid (1) may be heat-treated at a temperature in the range of 40°C or higher and 500°C or lower. According to this method, a laminate according to the present embodiment, which has a support and a polyimide film (specifically, a polyimide film containing an imidized product of polyamic acid (1)) disposed on the support, is obtained. be done.
  • a polyimide film specifically, a polyimide film containing an imidized product of polyamic acid (1)
  • the polyamic acid composition is directly put into a container that has been subjected to release treatment such as coating with a fluororesin, and the polyamic acid composition is heated and dried under reduced pressure to effect dehydration ring closure of the polyamic acid (1).
  • release treatment such as coating with a fluororesin
  • Polyimide can be obtained by dehydration ring closure of polyamic acid (1) by these techniques.
  • the heating time for each of the above treatments varies depending on the amount of the polyamic acid composition to be subjected to dehydration ring closure and the heating temperature, but is generally in the range of 1 minute or more and 300 minutes or less after the treatment temperature reaches the maximum temperature. It is preferable to
  • the polyimide film according to the present embodiment (specifically, the polyimide film containing the imidized product of polyamic acid (1)) is colorless and transparent, has a low degree of yellowness, and has a glass transition temperature (heat resistance) that can withstand the TFT manufacturing process. Therefore, it is suitable as a transparent substrate material for flexible displays.
  • the content of polyimide (specifically, imidized polyamic acid (1)) in the polyimide film according to the present embodiment is, for example, 70% by weight or more, and 80% by weight or more with respect to the total amount of the polyimide film. is preferable, more preferably 90% by weight or more, and may be 100% by weight.
  • components other than polyimide in the polyimide film include the additives described above (more specifically, nanosilica particles and the like).
  • An electronic device (more specifically, a flexible device or the like) according to this embodiment has a polyimide film according to this embodiment and an electronic element directly or indirectly arranged on this polyimide film.
  • an inorganic substrate such as glass is used as a support, and a polyimide film is formed thereon.
  • an electronic device is formed on the support by arranging (forming) an electronic element such as a TFT on the polyimide film.
  • the process of forming a TFT is generally carried out in a wide temperature range of 150° C. or higher and 650° C. or lower. is formed, and in some cases, a-Si or the like is further crystallized by a laser or the like.
  • the 1% weight loss temperature of polyimide is preferably 500° C. or higher because there is a possibility that a barrier film (to be described later) and electronic elements may peel off.
  • the upper limit of the 1% weight loss temperature of polyimide is preferably 600° C., for example, although the higher the better.
  • the 1% weight loss temperature can be adjusted, for example, by changing the content of residues having a rigid structure (more specifically, SFDA residues, BPDA residues, etc.).
  • an inorganic film such as a silicon oxide film (SiOx film) or a silicon nitride film (SiNx film) is formed as a barrier film on the polyimide film.
  • SiOx film silicon oxide film
  • SiNx film silicon nitride film
  • the polyimide and the inorganic film are separated from each other. Therefore, in addition to the 1% weight loss temperature of the polyimide being 500° C. or higher, the weight loss rate when the polyimide is kept isothermally at a temperature within the range of 400° C. or higher and 450° C. or lower must be less than 1%. desirable.
  • the present inventors' studies have revealed that polyimides obtained using fluorine-containing monomers generate corrosive gases such as hydrogen fluoride as outgassing in high-temperature processes such as the fabrication of TFT elements. .
  • the barrier film or the like laminated on the polyimide film corrodes, and peeling or the like may occur at the interface of the laminated body.
  • the fluorine atom content of polyamic acid (1) is preferably less than 1% by weight, more preferably less than 0.5% by weight, and more preferably less than 0.1% by weight. It is more preferably less than % by weight, and particularly preferably substantially 0 % by weight (polyamic acid (1) does not contain residues derived from fluorine-containing monomers).
  • the polyimide according to the present embodiment As an indicator of the amount of hydrogen fluoride gas generated when the imidized product of polyamic acid (1) (the polyimide according to the present embodiment) is used in a high-temperature process, detection intensity obtained from a mass spectrum can be mentioned. Specifically, first, the polyimide is heated from an atmospheric temperature of 60° C. at a rate of 10° C./min under a helium gas stream, and the gas generated from the polyimide when the atmospheric temperature reaches 470° C. Analyze with a type mass spectrometer.
  • the 20 peak intensity tends to increase as the amount of hydrogen fluoride generated increases.
  • the flow rate of the helium gas when analyzing with a quadrupole mass spectrometer may be set so that the gas generated from the polyimide can be analyzed in real time with the quadrupole mass spectrometer. minutes or more and 150 mL/minute or less, preferably 80 mL/minute or more and 120 mL/minute or less.
  • the glass transition temperature (Tg) of the polyimide is significantly lower than the process temperature, there is a possibility that misalignment or the like may occur during the formation of the electronic device. It is more preferably 350° C. or higher, still more preferably 400° C. or higher, and even more preferably 420° C. or higher.
  • the upper limit of Tg of polyimide is preferably 470° C., although the higher the better.
  • the coefficient of thermal expansion of the glass substrate is generally smaller than that of resin, internal stress is generated between the glass substrate and the polyimide film.
  • the laminated body including the polyimide film expands in the TFT formation process at a high temperature and then shrinks when cooled to room temperature.
  • the internal stress between the polyimide film and the glass substrate is preferably 40 MPa or less, more preferably 35 MPa or less.
  • the lower limit of the internal stress is better, and may be 0 MPa.
  • the method for measuring the internal stress is the same method as in Examples described later or a method based thereon.
  • the polyimide according to this embodiment can be suitably used as a material for display substrates such as TFT substrates and touch panel substrates.
  • an electronic device (more specifically, an electronic device having electronic elements formed on a polyimide film) is formed on a support as described above, and then the polyimide film is peeled off from the support. often adopted.
  • alkali-free glass is preferably used as the material of the support.
  • the polyamic acid composition according to the present embodiment is applied (cast) onto a support to form a coated film-containing laminate comprising a coated film containing polyamic acid (1) and the support.
  • the coated film-containing layered product is heated, for example, at a temperature of 40° C. or higher and 200° C. or lower.
  • the heating time at this time is, for example, 3 minutes or more and 120 minutes or less.
  • a multi-step heating process may be provided, such as heating the coating film-containing laminate at a temperature of 50° C. for 30 minutes and then heating it at a temperature of 100° C. for 30 minutes.
  • the coating film-containing laminate is heated, for example, at a maximum temperature of 200° C. or higher and 500° C. or lower.
  • the heating time (heating time at the maximum temperature) at this time is, for example, 1 minute or more and 300 minutes or less. At this time, it is preferable to gradually raise the temperature from the low temperature to the maximum temperature.
  • the heating rate is preferably 2° C./min or more and 10° C./min or less, more preferably 4° C./min or more and 10° C./min or less.
  • the maximum temperature is preferably in the range of 250° C. or higher and 450° C. or lower. When the maximum temperature is 250° C.
  • imidization proceeds sufficiently, and when the maximum temperature is 450° C. or lower, thermal deterioration and coloration of the polyimide can be suppressed. Also, any temperature may be maintained for any length of time until the maximum temperature is reached.
  • the imidization reaction can be carried out under air, under reduced pressure, or in an inert gas such as nitrogen, but in order to develop higher transparency, it is carried out under reduced pressure or in an inert gas such as nitrogen. is preferred.
  • the heating device known devices such as a hot air oven, an infrared oven, a vacuum oven, an inert oven and a hot plate can be used.
  • Polyamic acid (1) in the coating film is imidized through these steps, and a laminate of a support and a polyimide film (a film containing an imidized product of polyamic acid (1)) (that is, according to the present embodiment) laminate) can be obtained.
  • a known method can be used to peel off the polyimide film from the obtained laminate of the support and the polyimide film. For example, it may be peeled off by hand, or may be peeled off using a mechanical device such as a driving roll or a robot. Furthermore, a method of providing a release layer between a support and a polyimide film, a method of forming a silicon oxide film on a substrate having a large number of grooves, forming a polyimide film using the silicon oxide film as a base layer, and oxidizing the substrate and the polyimide film. A method of exfoliating the polyimide film by infiltrating a silicon oxide etchant between it and the silicon film can also be adopted. Alternatively, a method of separating the polyimide film by laser light irradiation may be employed.
  • the transparency of the polyimide film can be evaluated by total light transmittance (TT) according to JIS K7361-1:1997 and haze according to JIS K7136-2000.
  • the total light transmittance of the polyimide film is preferably 75% or more, more preferably 80% or more.
  • the haze of the polyimide film is preferably 1.5% or less, more preferably 1.2% or less, and 1.0%. It is more preferably less than, and may be 0%.
  • polyimide films are required to have high transmittance over the entire wavelength range. often colored.
  • the polyimide film is less colored.
  • the yellowness index (YI) of the polyimide film is preferably 25 or less, more preferably 20 or less, It can be 0.
  • YI can be measured according to JIS K7373-2006. YI can be adjusted, for example, by changing the content of SFDA residues in polyamic acid (1).
  • the polyimide film with reduced coloration and imparted with transparency is suitable for transparent substrates such as glass substitutes, and substrates on which a sensor or camera module is provided on the back surface.
  • the top emission method in which light is extracted from the front surface of the TFT
  • the bottom emission method in which light is extracted from the back surface of the TFT.
  • the top emission method light is not blocked by the TFT, so it is easy to increase the aperture ratio and obtain high-definition image quality. Characteristic. If the TFT is transparent, it is possible to improve the aperture ratio even in the bottom emission method, so there is a tendency to adopt the bottom emission method, which is easy to manufacture, for large displays. Since the polyimide film according to this embodiment has a low YI and excellent heat resistance, it can be applied to either of the above light extraction methods.
  • a polyamic acid composition is applied to a support such as a glass substrate, heated to imidize, an electronic element or the like is formed, and then the polyimide film is peeled off, the support and the like are used.
  • Adhesion means adhesion strength.
  • the manufacturing process of peeling off the polyimide film on which the electronic elements and the like are formed from the support after forming the electronic elements on the polyimide film on the support if the adhesion between the polyimide film and the support is excellent, the electronic element etc. can be formed or implemented more accurately.
  • the peel strength between the support and the polyimide film should be as high as possible from the viewpoint of improving productivity.
  • the peel strength is preferably 0.05 N/cm or more, more preferably 0.1 N/cm or more.
  • the polyimide film when peeling the polyimide film from the laminate of the support and the polyimide film, the polyimide film is often peeled off from the support by laser irradiation.
  • the cutoff wavelength of the polyimide film is required to be longer than the wavelength of the laser light used for peeling. Since a XeCl excimer laser with a wavelength of 308 nm is often used for laser peeling, the cutoff wavelength of the polyimide film is preferably 312 nm or longer, more preferably 330 nm or longer.
  • the cutoff wavelength of the polyimide film is preferably 390 nm or less.
  • the cutoff wavelength of the polyimide film is preferably 320 nm or more and 390 nm or less, more preferably 330 nm or more and 380 nm or less, from the viewpoint of achieving both transparency (low degree of yellowness) and workability of laser peeling.
  • the term "cutoff wavelength" as used herein means a wavelength at which the transmittance is 0.1% or less as measured by an ultraviolet-visible spectrophotometer.
  • the polyamic acid composition and polyimide according to the present embodiment may be used as they are for coating and molding processes for producing products and members, but the molded product molded in the form of a film is further subjected to coating and other treatments. It can also be used as a material for For use in coating or molding processes, the polyamic acid composition or polyimide, optionally dissolved or dispersed in an organic solvent, and optionally a photocurable component, a thermosetting component, a non-polymeric binder, A composition comprising polyamic acid (1) or polyimide may be prepared by blending the resin and other ingredients.
  • inorganic thin films such as metal oxide thin films and transparent electrodes may be formed on the surface of the polyimide film according to this embodiment.
  • the method for forming these inorganic thin films is not particularly limited, and examples thereof include PVD methods such as sputtering, vacuum deposition, and ion plating, and CVD methods.
  • the polyimide film according to the present embodiment In addition to heat resistance, low thermal expansion, and transparency, the polyimide film according to the present embodiment generates little internal stress when forming a laminate with a glass substrate, ensuring adhesion with inorganic materials during high-temperature processes. Therefore, it is preferably used in fields and products where these properties are useful.
  • the polyimide film according to the present embodiment can be used for liquid crystal display devices, organic EL devices, image display devices such as electronic paper, printed matter, color filters, flexible displays, optical films, 3D displays, touch panels, transparent conductive film substrates, solar cells, and the like. It is more preferable to use it as a substitute material for parts where glass is currently used.
  • the thickness of the polyimide film is, for example, 1 ⁇ m or more and 200 ⁇ m or less, preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the polyimide film can be measured using a laser hologram.
  • the polyamic acid composition according to the present embodiment is prepared by coating the polyamic acid composition on a support, imidizing it by heating, forming an electronic element or the like, and then peeling off the polyimide film for batch-type device fabrication. It can be suitably used for the process. Therefore, in the present embodiment, a method for producing an electronic device includes a step of applying a polyamic acid composition onto a support, imidizing it by heating, and forming an electronic element or the like on a polyimide film formed on the support. is also included. Moreover, the method for producing such an electronic device may further include a step of peeling off the polyimide film on which the electronic elements and the like are formed from the support.
  • the internal stress generated between the glass substrate and the polyimide film was calculated from the amount of warpage of the glass substrate before the formation of the polyimide film and the amount of warpage of the laminate by the Stoney equation.
  • the internal stress was 40 MPa or less, it was evaluated as "the internal stress can be reduced.”
  • the internal stress exceeded 40 MPa, it was evaluated as "the internal stress cannot be reduced.”
  • Glass transition temperature (Tg) A polyimide film having a width of 3 mm and a length of 10 mm was sampled from each laminate obtained in Examples and Comparative Examples, which will be described later, and used as a sample for Tg measurement. Using a thermal analysis device ("TMA/SS7100" manufactured by Hitachi High-Tech Science), a load of 29.8 mN was applied to the sample, the temperature was raised from 20 ° C. to 500 ° C. at 10 ° C./min, and the temperature and strain amount (elongation ) to obtain the TMA curve. The temperature at the inflection point of the obtained TMA curve (the temperature corresponding to the peak in the differential curve of the TMA curve) was defined as the glass transition temperature (Tg). When Tg was 420°C or higher, it was evaluated as “excellent in heat resistance”. On the other hand, when Tg was less than 420°C, it was evaluated as "not excellent in heat resistance”.
  • TD1 1% weight loss temperature
  • NMP N-methyl-2-pyrrolidone SFDA: spiro[11H-diflo[3,4-b:3′,4′-i]xanthene-11,9′-[9H]fluorene]-1,3,7, 9-Tetrone
  • SFDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • BPAF 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • 6FDA 4,4′-( Hexafluoroisopropylidene) diphthalic anhydride
  • PDA p-phenylenediamine 4-BAAB: 4-aminophenyl-4-aminobenzoate
  • DABA 4,4'-diaminobenzanilide
  • DATA N,N'-di(4-amino Phenyl)terephthalamide
  • PAM-E 1,3-bis(3-aminopropyl)t
  • Example 1 A 300 mL glass separable flask equipped with a stirrer with a stainless steel stir bar and a nitrogen inlet was charged with 88.0 g of NMP as an organic solvent for polymerization. 2.240 g of PDA was then added to the flask and dissolved while stirring the flask contents. After adding 9.760 g of SFDA to the contents of the flask, the contents of the flask were stirred for 24 hours under an atmosphere of 25° C. to obtain a polyamic acid composition.
  • the resulting polyamic acid composition was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm x 100 mm) using a spin coater, and coated in air at 120°C. After heating for 30 minutes, it was heated at 430° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate (laminate of Example 1) having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
  • Example 2 A 300 mL glass separable flask equipped with a stirrer with a stainless steel stir bar and a nitrogen inlet was charged with 88.0 g of NMP as an organic solvent for polymerization. 2.240 g of PDA was then added to the flask and dissolved while stirring the flask contents. After adding 9.760 g of SFDA to the contents of the flask, the contents of the flask were stirred for 24 hours under an atmosphere at a temperature of 25°C. Next, DMI was added to the contents of the flask to obtain a polyamic acid composition. The amount of DMI added was 1 part by weight per 100 parts by weight of polyamic acid in the contents of the flask.
  • the resulting polyamic acid composition was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm x 100 mm) using a spin coater, and coated in air at 120°C. After heating for 30 minutes, it was heated at 430° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate (laminate of Example 2) having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
  • Examples 3 to 17 and Comparative Examples 1 to 8 Examples 3, 5, and 6 were prepared in the same manner as in Example 1, except that the acid dianhydride used and its charging ratio, and the diamine used and its charging ratio were as shown in Tables 1 and 2. , 8, 10, 12, 13, 15 and 17 and the laminates of Comparative Examples 1, 2, 3 and 5, respectively. In addition, in the same manner as in Example 2, except that the acid dianhydride used and its charging ratio, and the diamine used and its charging ratio were as shown in Tables 1 and 2, Examples 4 and 7 , 9, 11, 14 and 16 and the laminates of Comparative Examples 4, 6, 7 and 8, respectively.
  • Table 3 shows the measurement results of the physical properties of Examples 1 to 17 and Comparative Examples 1 to 8.
  • "-" means not measured.
  • the "fluorine atom content” is a calculated value calculated by the above formula.
  • the polyamic acid in the polyamic acid compositions prepared in Examples 1 to 17 contained the structural unit (1) and had a fluorine atom content of 5% by weight or less. As shown in Table 3, in Examples 1 to 17, the internal stress was 40 MPa or less. Therefore, the polyimides obtained in Examples 1 to 17 were able to reduce the internal stress. Examples 1-17 had a haze of less than 1.0%. Therefore, the polyimides obtained in Examples 1 to 17 were excellent in transparency. In Examples 1 to 17, Tg was 420° C. or higher. Therefore, the polyimides obtained in Examples 1 to 17 were excellent in heat resistance.
  • the polyamic acid in the polyamic acid compositions prepared in Comparative Examples 1 and 2 had a fluorine atom content of more than 5% by weight.
  • the polyamic acid in the polyamic acid compositions prepared in Comparative Examples 3-8 did not contain the structural unit (1).
  • the internal stress exceeded 40 MPa. Therefore, the polyimides obtained in Comparative Examples 1, 2 and 6-8 could not reduce the internal stress.
  • the Tg was less than 420°C. Therefore, the polyimides obtained in Comparative Examples 3 to 5 were not excellent in heat resistance.
  • the polyimide obtained from the polyamic acid composition according to the present invention has excellent transparency and heat resistance while reducing internal stress.

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

Abstract

La présente invention concerne, un acide polyamique qui comprend une unité structurale représentée par la formule générale (1) et a une teneur en atomes de fluor ne dépassant pas 5 % en poids. Dans la formule générale (1), R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un groupe aliphatique monovalent ou un groupe aromatique monovalent, et X1 représente un groupe organique bivalent. Selon la présente invention, une composition d'acide polyamique contient un solvant organique et un acide polyamique qui comprend une unité structurale représentée par la formule générale (1) et a une teneur en atomes de fluor ne dépassant pas 5 % en poids. Selon la présente invention, un polyimide est un composé imide d'un acide polyamique qui comprend une unité structurale représentée par la formule générale (1) et a une teneur en atomes de fluor ne dépassant pas 5 % en poids.
PCT/JP2022/025343 2021-07-01 2022-06-24 Acide polyamique, composition d'acide polyamique, polyimide, film de polyimide, stratifié, procédé de production de stratifié et dispositif électronique WO2023276888A1 (fr)

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CN202280046631.XA CN117580893A (zh) 2021-07-01 2022-06-24 聚酰胺酸、聚酰胺酸组合物、聚酰亚胺、聚酰亚胺膜、层叠体、层叠体的制造方法和电子器件

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016148150A1 (fr) * 2015-03-17 2016-09-22 田岡化学工業株式会社 Nouveau dianhydride tétracarboxylique, et polyimide et copolymère de polyimide obtenus à partir dudit dianhydride d'acide
WO2019195148A1 (fr) * 2018-04-06 2019-10-10 E. I. Du Pont De Nemours And Company Polymères destinés à être utilisés dans des dispositifs électroniques
JP2022061487A (ja) * 2020-10-06 2022-04-18 東レ株式会社 樹脂組成物、それを用いた表示デバイスまたは受光デバイスの製造方法、基板ならびにデバイス

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JP5903789B2 (ja) 2010-07-22 2016-04-13 宇部興産株式会社 共重合ポリイミド前駆体及び共重合ポリイミド
JP6086139B2 (ja) 2015-10-05 2017-03-01 宇部興産株式会社 ポリイミド前駆体及びポリイミド

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016148150A1 (fr) * 2015-03-17 2016-09-22 田岡化学工業株式会社 Nouveau dianhydride tétracarboxylique, et polyimide et copolymère de polyimide obtenus à partir dudit dianhydride d'acide
WO2019195148A1 (fr) * 2018-04-06 2019-10-10 E. I. Du Pont De Nemours And Company Polymères destinés à être utilisés dans des dispositifs électroniques
JP2022061487A (ja) * 2020-10-06 2022-04-18 東レ株式会社 樹脂組成物、それを用いた表示デバイスまたは受光デバイスの製造方法、基板ならびにデバイス

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