WO2015125895A1 - Polyimide precursor and/or polyimide-containing composition, and polyimide film - Google Patents

Polyimide precursor and/or polyimide-containing composition, and polyimide film Download PDF

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Publication number
WO2015125895A1
WO2015125895A1 PCT/JP2015/054691 JP2015054691W WO2015125895A1 WO 2015125895 A1 WO2015125895 A1 WO 2015125895A1 JP 2015054691 W JP2015054691 W JP 2015054691W WO 2015125895 A1 WO2015125895 A1 WO 2015125895A1
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polyimide
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less
formula
tetracarboxylic acid
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PCT/JP2015/054691
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French (fr)
Japanese (ja)
Inventor
美香 山口
二郎 杉山
野口　浩
智子 古賀
章 石窪
剛司 加藤
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三菱化学株式会社
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Priority to JP2015538174A priority Critical patent/JP5888472B2/en
Priority to CN201580009667.0A priority patent/CN106029743B/en
Priority to KR1020167022628A priority patent/KR102268406B1/en
Publication of WO2015125895A1 publication Critical patent/WO2015125895A1/en

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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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the present invention includes a polyimide precursor and / or a polyimide composition having a specific partial structure, a polyimide precursor composition that suppresses whitening of the film when forming a film, a specific partial structure, heat resistance,
  • the present invention relates to a polyimide and a polyimide film excellent in transmittance, low linear expansion coefficient and low retardation.
  • Patent Document 1 mentions a polyimide material having heat resistance and little dimensional change (small linear expansion coefficient).
  • Patent Document 2 proposes an amideimide material having an amide bond.
  • Patent Document 1 when the monomer constituting the polyimide is only an aromatic compound, the in-plane orientation is strong, the retardation is high, and a phase difference is generated. If a material that generates such a phase difference is used, for example, the front view of the display or the visual field in an oblique direction tends to deteriorate. Moreover, when it has an amide bond like the amide imide material proposed by patent document 2, since an amide bond has high water absorption and solvent affinity, it exists in the tendency for the hydrolyzability of the polyimide resin obtained to become high. . As described above, no material has been proposed that simultaneously satisfies heat resistance, transmittance, low linear expansion coefficient, and low retardation, which are characteristics necessary for application to device materials.
  • the present invention has been accomplished in view of the above problems, and is to provide a polyimide material excellent in heat resistance, transmittance, low linear expansion coefficient and low retardation.
  • the present invention has the following configuration.
  • [1] A polyimide film containing a tetracarboxylic acid residue and a diamine residue, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bent portion, and the linear expansion coefficient is 60 ppm / K or less And the retardation is 200 nm or less, The polyimide film characterized by the above-mentioned.
  • X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
  • R 3 and R 4 are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
  • the ratio of the tetracarboxylic acid residue having the partial structure represented by the formula (4 ′) in the tetracarboxylic acid residue is 2 mol% or more and 95 mol% or less.
  • Composition. [5] A tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) and a tetracarboxylic acid residue having a partial structure represented by the formula (2) in the tetracarboxylic acid residue.
  • the composition according to the above [3] or [4], wherein the sum ratio is 5 mol% or more and 95 mol% or less.
  • a polyimide precursor and / or a polyimide composition a polyimide and a polyimide film which are excellent in heat resistance, transmittance, low linear expansion coefficient and low retardation.
  • composition of the present invention is a composition containing at least one of a polyimide precursor and a polyimide, and the polyimide precursor and / or polyimide contains a tetracarboxylic acid residue and a diamine residue, and the tetracarboxylic acid
  • the acid residue has a partial structure selected from one or more from group I shown below and a partial structure selected from one or more from group II shown below, wherein the diamine residue is represented by the following formula (5): It is a composition characterized by having the partial structure represented by these.
  • X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group.
  • n and m each independently represent 0 or 1.
  • R 1 and R 2 each independently represents an alkylene group, an alkenylene group or an aromatic ring. R 1 and R 2 may be bonded to each other to form a ring.
  • Y represents a direct bond or a divalent organic group.
  • R 3 and R 4 each independently represents an alkyl group, an alkoxy group, an amino group or a hydroxyl group.
  • the tetracarboxylic acid residue has a partial structure selected from one or more from group I and a partial structure selected from one or more from group II, and the diamine residue has a partial structure represented by formula (5)
  • the following is estimated as a reason for having the effect of the present invention.
  • the tetracarboxylic acid residue selected from Group I and the diamine residue represented by the formula (5) the effects of improving heat resistance and mechanical properties and lowering the linear expansion coefficient can be obtained.
  • the in-plane orientation tends to be strong and the retardation tends to be high, but by having a tetracarboxylic acid residue selected from Group II, these effects can be achieved.
  • the tetracarboxylic acid residue represents a tetravalent group derived from tetracarboxylic dianhydride.
  • a diamine residue represents the bivalent group induced
  • the partial structure selected from the group I is a partial structure represented by the following formula (1 ′) and a partial structure represented by the formula (2), and is selected from the group II
  • the partial structure represented by the following formula (4 ′) and the partial structure of the diamine residue being the partial structure represented by the following formula (5) balance the linear expansion coefficient and the optical characteristics. It is preferable because it is easy to remove, and it is more preferable that at least one of the tetracarboxylic acid residue and the diamine residue has a bending site. Details of each partial structure and bending portion will be described later.
  • X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
  • R 3 and R 4 are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
  • composition of the present invention may contain other components in addition to the polyimide precursor and / or polyimide.
  • an imidizing agent can be added in order to further increase the imidization rate during film formation.
  • the polyimide precursor and / or polyimide contained in the composition according to the present invention includes a tetracarboxylic acid residue and a diamine residue.
  • the tetracarboxylic acid residue has a partial structure selected from one or more groups from group I and a partial structure selected from one or more groups from group II.
  • the partial structure represented by formula (5) as the diamine residue If it has, it will not specifically limit. These are preferably compounds soluble in a solvent.
  • the composition of the present invention may have a polyimide precursor and / or a polyimide that does not have a partial structure of Group I or Group II as a tetracarboxylic acid residue. Moreover, you may have what does not have the partial structure represented by Formula (5) as a diamine residue.
  • “soluble in a solvent” means complete dissolution when a polyimide precursor and / or polyimide is dissolved at 0.5% by mass at room temperature (25 ° C.) in a solvent constituting the composition. To do.
  • the concentration for complete dissolution is usually 0.5% by mass or more, preferably 1% by mass or more, and more preferably 10% by mass or more.
  • the solvent constituting the composition include a solvent used for obtaining a polyimide precursor and polyimide contained in the composition of the present invention described later, a solvent used for reprecipitation, and the like.
  • the concentration of the polyimide precursor and / or polyimide in the composition can be appropriately confirmed using a conventionally known method.
  • the solvent of the composition can be obtained by distillation using a method such as drying under reduced pressure, and the mass ratio before and after the distillation.
  • the concentration of the composition is less than 0.5% by mass, the composition can be concentrated using a method such as distilling off the solvent under reduced pressure to determine whether or not the composition is soluble in the solvent.
  • the concentration of the composition is high, the concentration can be made 0.5 mass% by diluting with the solvent of the composition.
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone
  • aprotic solvents such as dimethyl sulfoxide
  • anisole It can be diluted with aromatic solvents such as cresol, xylene and toluene, glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate.
  • the tetracarboxylic acid residue examples include partial structures of Group I and Group II.
  • the tetracarboxylic acid residue is not particularly limited as long as it has a partial structure selected from one or more groups from group I and a partial structure selected from one or more groups from group II.
  • it has a plurality of partial structures from group I.
  • And may have a plurality of partial structures represented by the formula (1).
  • the group I since the effect of lowering the linear expansion coefficient is high, it preferably has a partial structure represented by the formula (1), and is represented by the partial structure represented by the formula (1) and the formula (2). It is more preferable to have both of the partial structures to be obtained because the heat resistance, the mechanical properties, and the linear expansion coefficient tend to be obtained. Further, in the group II, it is preferable to have a partial structure represented by the formula (4) in order to improve optical characteristics.
  • the ratio of the tetracarboxylic acid residues having a partial structure selected from each group of Group I and Group II among tetracarboxylic acid residues contained in the composition of the present invention is not particularly limited, but is usually 10 mol. % Or more, preferably 30 mol% or more, more preferably 50 mol% or more. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
  • the ratio of the tetracarboxylic acid residue having a partial structure selected from Group I and the tetracarboxylic acid residue having a moiety selected from Group II is not particularly limited.
  • the proportion of the tetracarboxylic acid residues having a partial structure selected from Group I is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
  • the ratio of the tetracarboxylic acid residue having a partial structure selected from Group I and the tetracarboxylic acid residue having a partial structure selected from Group II is not particularly limited. It is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and is usually 500 mol% or less, preferably 300 mol% or less, more preferably 200 mol% or less, and even more preferably 150 mol% or less.
  • the ratio of the sum of the residue and the tetracarboxylic acid residue having the partial structure represented by the formula (4 ′) is not particularly limited, but is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol%. That's it. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
  • the ratio with the tetracarboxylic acid residue is not particularly limited.
  • the ratio of the sum occupied by the residues is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less.
  • the absorption near 308 nm and 355 nm used for laser processing increases, and it can be compatible with laser processing.
  • the ratio with the tetracarboxylic acid residue is not particularly limited, but the tetracarboxylic acid residue having the partial structure represented by the formula (1 ′) and the tetracarboxylic acid residue having the partial structure represented by the formula (2)
  • the proportion of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) relative to the sum of the groups, is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 500 mol% or less.
  • the proportion of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) in the tetracarboxylic acid residue contained in the composition of the present invention is usually 2 mol% or more, preferably 5 mol% or more, More preferably, it is 8 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
  • the ratio of the tetracarboxylic acid residue having a partial structure represented by the formula (2) to the tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) is not particularly limited, but is usually 0.5 mol. % Or more, preferably 1 mol% or more, more preferably 3 mol% or more, and usually 500 mol% or less, preferably 400 mol% or less, more preferably 300 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
  • the ratio of the tetracarboxylic acid residue to the sum is not particularly limited, but is usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually 95 mol% or less, preferably 90 mol% or less, more preferably It is 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
  • the ratio of the tetracarboxylic acid residue can be determined by analyzing the composition of the raw material monomer by NMR, solid NMR, IR, or the like. Further, after dissolution with alkali, it can be determined by gas chromatography (GC), 1 H-NMR, 13 C-NMR, two-dimensional NMR, mass spectrometry, and the like.
  • GC gas chromatography
  • the ratio of the diamine residue having a partial structure represented by the formula (5) in the diamine residue is not particularly limited, but is usually 0.1 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more. More preferably, it is 7 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol% or more. Moreover, there is no upper limit in particular and 100 mol% may be sufficient.
  • a polyimide precursor and / or a polyimide composition for obtaining a polyimide having a low linear expansion coefficient is obtained by including a specific amount or more of the diamine residue having the partial structure represented by the formula (5) in the diamine residue. be able to.
  • the amount of the diamine compound for inducing the diamine residue is usually 0.7 mol or more, preferably 0.8 mol or more, usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. It is. By setting the amount of the diamine compound within this range, a polyimide precursor and / or a polyimide having an appropriate molecular weight can be obtained.
  • Group I (Group I and Group II) Group I: The following formulas (1) and (2) are shown.
  • X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group.
  • n and m each independently represent 0 or 1
  • R 1 and R 2 each independently represents an alkylene group, an alkenylene group or an aromatic ring.
  • R 1 and R 2 may be different or the same, and may form a ring.
  • Y represents a direct bond or a divalent organic group.
  • X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group.
  • X is preferably a direct bond, a carbonyl group or a sulfonyl group, and more preferably a direct bond, since the effect of lowering the linear expansion coefficient is high.
  • the alkylene group is not particularly limited, but preferably has 1 or more carbon atoms, more preferably 2 or more. On the other hand, it is preferably 8 or less, and more preferably 5 or less. Moreover, the said alkylene group may have a substituent, for example, an amino group, a hydroxyl group, a halogen atom, etc. are mentioned.
  • the tetracarboxylic acid residue having a partial structure represented by the formula (1) is not particularly limited.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, Tetracarboxylic dianhydrides in which X is a direct bond such as 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride; bis (3,4-di Carboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,3,3 ′, 4′-tetracarboxyphenylmethane dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2- (2,3,3 ', 4'-te
  • Carboxylic dianhydride 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, , 3'-diphenylsulfone tetracarboxylic dianhydride
  • X is tetracarboxylic dianhydride is sulfonyl group; tetracarboxylic acid residue and the like which are derived from tetracarboxylic dianhydride such.
  • the partial structure represented by the formula (1) of the tetracarboxylic acid residue is the partial structure represented by the following formula (1 ′), which improves the heat resistance and mechanical properties and lowers the linear expansion coefficient. Is preferable because it tends to be obtained.
  • X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond, and among these, a direct bond is preferable because mechanical properties are improved. Moreover, in the polyimide film obtained from the composition, absorption near 308 nm and 355 nm used for laser processing is increased, which is preferable because it can be applied to laser processing.
  • the bond having a secondary or tertiary carbon atom means that X 2 is a secondary or tertiary carbon atom having 1 carbon atom.
  • the carbon atom of X 2 is linked to a hydrogen atom and / or a substituent other than being linked to the benzene ring in formula (1 ′). Examples of the substituent connected to the carbon atom of X 2 include a halogen atom, a cyano group, a nitro group, and a sulfo group.
  • Tetracarboxylic acid residue having a partial structure represented by formula (2) examples include pyromellitic dianhydride.
  • n and m each independently represent 0 or 1. Although not particularly limited, at least one of n and m is preferably 1 from the viewpoint of imidization reactivity.
  • R 1 and R 2 each independently represents an alkyl group, an alkenyl group or an aromatic ring. R 1 and R 2 may be different or the same, and may form a ring. Moreover, the alkyl group, the alkenyl group, and the aromatic ring may have a substituent.
  • C1 or more is preferable each independently. On the other hand, 10 or less is preferable, and 8 or less is more preferable.
  • the aromatic ring may be either a single ring or a condensed ring. Specifically, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned. In particular, a benzene ring is preferable because the solubility in an organic solvent tends to be high.
  • the tetracarboxylic acid residue having a partial structure represented by the formula (3) is not particularly limited.
  • Y represents a direct bond or a divalent organic group.
  • a bivalent organic group For example, an alkylene group, a carbonyl group, an ether bond, a sulfonyl group etc. are mentioned.
  • Y has a tendency to improve optical characteristics, and therefore, direct bonding is preferable.
  • the said alkylene group is synonymous with the preferable range of the alkylene group of X of Formula (1), and the substituent which you may have is also synonymous.
  • the tetracarboxylic acid residue having a partial structure represented by the formula (4) is not particularly limited.
  • bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride, bicyclohexane-2 , 3,3 ′, 4′-tetracarboxylic dianhydride, tetracarboxylic dianhydrides such as bicyclohexane-2,2 ′, 3,3′-tetracarboxylic dianhydride Examples include residues.
  • a tetracarboxylic acid residue derived from bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride is preferable because optical properties tend to be improved.
  • the partial structure represented by the formula (4) of the tetracarboxylic acid residue is preferably a partial structure represented by the following formula (4 ') because the optical properties are improved.
  • diamine residue examples include a partial structure represented by the formula (5).
  • R ⁇ 3 > and R ⁇ 4 > shows an alkyl group, an alkoxy group, an amino group, or a hydroxyl group each independently.
  • R 3 and R 4 each independently represents an alkyl group, an alkoxy group, an amino group, or a hydroxyl group.
  • the alkyl group and the alkoxy group each independently preferably have 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low.
  • the alkyl group and the alkoxy group may each have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group.
  • R 3 and R 4 are preferably an alkyl group or an alkoxy group because optical characteristics and a linear expansion coefficient are improved, and an alkyl group having a halogen atom as a substituent tends to have a low linear expansion coefficient. Therefore, it is more preferable.
  • R 3 and R 4 may be the same or different, but are preferably the same from the viewpoint of ease of production.
  • the diamine residue having a partial structure represented by the formula (5) is not particularly limited.
  • R such as 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-diamino-2,2′-diethylbiphenyl, 4,4′-diamino-2,2′-dipropylbiphenyl, etc.
  • the diamine of having R 3 and R 4 are alkoxy groups such as 4,4'-diamino-2,2'-dihydroxybiphenyl with Things; the diamine residue derived from a diamine compound such like.
  • the composition according to the present invention has a partial structure represented by the formula (1 ′), the formula (2), the formula (4 ′) and the formula (5), a tetracarboxylic acid residue and a diamine residue.
  • a tetracarboxylic acid residue having other than the partial structure represented by formula (1 ′), formula (2), formula (4 ′) and formula (5) Other than the tetracarboxylic acid residues derived from tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides shown below and partial structures represented by formula (3) The tetracarboxylic acid residue which has is mentioned.
  • aromatic tetracarboxylic dianhydride examples include tetracarboxylic dianhydrides having one aromatic ring in the molecule such as 1,2,3,4-benzenetetracarboxylic dianhydride; , 2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylene) -diphthalic dianhydride, 4,4 '-(octafluo
  • aliphatic tetracarboxylic dianhydride examples include alicyclic tetracarboxylic acids such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Dianhydrides; chain aliphatic tetracarboxylic dianhydrides such as ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride And the like.
  • a diamine residue derived from a diamine compound shown below can be used as a diamine residue having a structure other than the partial structure represented by the formula (5) without departing from the gist of the present invention.
  • diamine compounds examples include diamine compounds having one aromatic ring contained in the molecule such as 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine; -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, bis (4 -Amino-3-carboxyphenyl) methane, 4,4'-diaminodiphenylsulfone, 4,4'-di Minodiphenyl sulfide,
  • diamine residues having other than the partial structure represented by formula (5) it is preferable to have a diamine residue having a partial structure represented by formula (6) in order to improve optical properties.
  • Z represents a direct bond, a sulfonyl group, an alkylene group, a carbonyl group or an ether bond
  • a and B each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group.
  • a sulfonyl group, an ether bond or a carbonyl group is preferable, and a sulfonyl group is more preferable in order to further improve optical properties.
  • the alkylene group for Z is not particularly limited, but preferably has 1 or more carbon atoms, more preferably 2 or more. On the other hand, it is preferably 8 or less, and more preferably 5 or less.
  • a and B each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group.
  • the divalent aromatic ring and the divalent heterocyclic ring may have a substituent.
  • phenyl ether groups are preferred because they tend to be highly soluble in solvents.
  • a and B may be the same or different, but the same is preferable from the viewpoint of ease of production.
  • divalent aromatic rings A and B include a benzene ring, a naphthalene ring, and an anthracene ring.
  • a benzene ring is preferable because the solubility in a solvent tends to be high.
  • divalent heterocycle of A and B include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, and benzoxazole.
  • Examples of the diamine residue having a partial structure represented by the formula (6) include 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 3,3 Diamine compounds in which Z is a direct bond such as' -bis (4-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl; 3,3'-diaminodiphenylsulfone, 4,4'-diamino Diphenylsulfone, 3,4'-diaminodiphenylsulfone, 2,3'-diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3 A diamine compound wherein Z is a sulfonyl group, such as -aminophenoxy) phenyl)
  • a diamine residue derived from a diamine compound such as a diamine compound in which Z is an ether bond; It is.
  • the bending portion is a bending portion in which deformation is suppressed, and a ring bond angle around the bending portion, a ring surface angle bonded to the bending portion, a tetracarboxylic acid residue such as rotation, vibration, etc. And / or those that suppress the movement of molecules containing diamine residues. Among them, those that suppress the ring coupling angle and rotational movement around the bent portion are preferable.
  • the bent portion is preferably a trivalent or higher group that is directly bonded to the ring structure and the ring structure, and the bond angle between the ring structures is less than 180 degrees, preferably 160 degrees or less, more preferably 130 degrees. It is as follows. There is no particular lower limit, but it is usually 90 degrees or more. The angle can be obtained by a conventionally known calculation method.
  • empirical molecular orbital methods such as Hückel method and extended Huckel method, Hartley Fock method, configuration substitution interaction method, ab initio molecular orbital methods such as multi-configuration SCF method, PPP approximation, CNDO / 2, INDO, MNDO And semi-empirical molecular orbital methods such as AM1 and PM3, molecular dynamics methods such as MM2, and density functional methods such as BLYP and B3LYP.
  • the present invention by having a bent portion, thermal vibration of the polyimide precursor and / or the entire polyimide chain is suppressed, and the linear expansion coefficient tends to be improved. Furthermore, by suppressing the interaction between the polyimide precursor and / or the polyimide chain, the optical properties such as transmittance and YI tend to be improved, and the regular orientation of the same chain is disturbed, Retardation tends to improve. Further, entanglement of molecular chains of the polyimide precursor and / or polyimide increases, and the amount of aromatic rings in the chain increases, so that the heat resistance tends to be improved.
  • the polyimide precursor and / or polyimide in the composition of the present invention may have both a tetracarboxylic acid residue and a diamine residue, which usually have a bending site, and a tetracarboxylic acid having a bending site. It may have a residue or a diamine residue. Among these, since the optical properties tend to be improved, the diamine residue preferably has a bent portion. In addition, it is preferable that the tetracarboxylic acid residue and the diamine residue have a bent portion because the optical characteristics tend to be improved.
  • a tetracarboxylic acid residue and / or diamine residue bending portion may have a plurality of bending portions, but the plurality of bending portions are preferably not connected. It exists in the tendency which can maintain and improve polymerizability by a bending part not connecting.
  • it is preferable that a cyclic structure is directly bonded to the bent portion. By directly bonding the annular structure, deformations such as a bonding angle, a surface angle of a ring bonded to a bent portion, rotation, vibration, and the like are further suppressed.
  • the cyclic structure directly bonded to the bending site may be derived from the same tetracarboxylic acid residue / diamine residue as the bending site or may be different.
  • the cyclic structure When derived from the same tetracarboxylic acid residue / diamine residue as that of the bent part, the cyclic structure is a structure possessed by the tetracarboxylic acid monomer / diamine monomer.
  • the cyclic structure is a cyclic imide structure.
  • the tetracarboxylic acid residue having a bent portion may be a tetracarboxylic acid residue having a partial structure represented by the above formula (1), formula (2), formula (3) and formula (4), It may be a tetracarboxylic acid residue having other than the partial structure represented by formula (1), formula (2), formula (3) and formula (4).
  • the tetracarboxylic acid residue having a bent portion is preferably represented by the formula (1), the formula (2), the formula (3), and the formula (4). It is a tetracarboxylic acid residue having other than a partial structure.
  • the tetracarboxylic acid residue having a bent portion is other than the partial structure represented by the above formula (1 ′), formula (2) and formula (4 ′). It is a tetracarboxylic acid residue having Moreover, you may have two or more tetracarboxylic acid residues which have a bending part.
  • the diamine residue having a bent portion is other than the partial structure represented by the above formula (5), and may have a plurality.
  • the content of the bent portion is not particularly limited, but is usually 0.1 mol% or more, preferably 0.5 mol%, more preferably 1 mol%, based on the ratio of the tetracarboxylic acid residue and the diamine residue in the composition. As mentioned above, More preferably, it is 5 mol% or more. Moreover, it is 150 mol% or less normally, Preferably it is 100 mol% or less, More preferably, it is 50 mol% or less. By being in these ranges, the optical properties are improved and the mechanical properties tend to be improved.
  • the element constituting the main chain bonded to the ring has a trivalent or higher bond.
  • the trivalent or higher bonds at least one selected from a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine, and a benzene ring is preferable.
  • the optical properties are improved when the tetracarboxylic acid and / or diamine residue having a bent portion is one in which two or more aromatic rings are bonded by a quaternary carbon atom and / or a hexavalent sulfur atom. This is preferable.
  • Those having a bond of 3 or more are not particularly limited as long as they do not depart from the gist of the present invention, and examples thereof include a structure represented by the following formula (30).
  • Z 1 represents a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine or a benzene ring.
  • Y 1 and Y 2 each independently represent a cyclic structure.
  • the quaternary carbon hexafluoropropane, propane, fluorene and the like are preferable because optical characteristics are improved.
  • hexavalent sulfur a sulfonyl group is preferable because optical characteristics are improved.
  • Trimethylamine is preferred as the tertiary amine.
  • the cyclic structure of Y 1 and Y 2 represents an aromatic compound, an alicyclic compound, or an imide ring.
  • the aromatic compound the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a condensed aromatic ring or a heterocyclic ring.
  • the number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
  • the heterocyclic ring is not particularly limited, and specific examples include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
  • substituents that the aromatic compound may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a hydroxyl group.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may have a substituent.
  • Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group. Examples of the substituent that the alkoxy group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
  • the alicyclic compound has 4 or more and 8 or less carbon atoms forming one ring, and a single ring or two rings may be condensed. Moreover, you may have an unsaturated bond in the ring. Specific examples include cyclobutane, cyclobutadiene, cyclopentane, cyclopentaene, cyclohexane, cyclohexaene, cyclohexadiene, cycloheptane, cycloheptaene, cyclooctane, and the like.
  • the alicyclic compound may have a substituent, and examples of the substituent that may be included include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino group. Group, hydroxyl group and the like.
  • the alkyl group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 6 or less carbon atoms may have a substituent, and examples of the substituent that may have may include the above-mentioned aromatic compounds. Synonymous with things.
  • An imide ring is a ring having an imide bond, and the number of elements forming one ring is 4 or more and 6 or less, and may be only an imide ring or may be condensed with another ring.
  • the ring which may be condensed includes an aromatic compound which may have a substituent and an alicyclic compound which may have a substituent.
  • the number of rings in the case of condensation is not particularly limited, but is preferably 2 or more and 4 or less because heat resistance and optical properties tend to be compatible.
  • a site selected from the structures represented by the following formulas (31) to (35) is preferable from the viewpoint of improving optical properties.
  • R 10 and R 11 each independently represents an alkyl group, an amino group or a hydroxyl group, and Y 1 and Y 2 each independently represent an aromatic hydrocarbon, an alicyclic compound or an imide ring.
  • the alkyl group for R 10 and R 11 preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low.
  • the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group.
  • Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
  • R 12 to R 15 each independently represents an alkyl group or a hydroxyl group.
  • the alkyl groups for R 12 to R 15 each independently preferably have 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low.
  • the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, it is preferable to have a halogen atom, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
  • Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
  • Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
  • R 16 represents an alkyl group or an aromatic compound.
  • Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
  • the alkyl group for R 16 preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low.
  • the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group.
  • the linear expansion coefficient tends to be low.
  • the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed.
  • it is a benzene ring, a condensed aromatic ring or a heterocyclic ring.
  • a monocyclic benzene ring or a condensed aromatic ring obtained by condensing a benzene ring is preferable because the coefficient of linear expansion tends to be low.
  • the number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
  • the heterocyclic ring is not particularly limited, and specific examples include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
  • Examples of the substituent that the aromatic compound may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a hydroxyl group.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may have a substituent.
  • Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group. Examples of the substituent that the alkoxy group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
  • R represents an alkyl group, a nitro group, an amino group, a hydroxyl group or a halogen atom.
  • the alkyl group is not particularly limited, but preferably has 1 or more carbon atoms. On the other hand, it is preferably 8 or less, and more preferably 5 or less. By being in these ranges, the compatibility with the solvent tends to be improved.
  • the alkyl group may have a substituent, and examples thereof include an amino group, a hydroxyl group, a nitro group, and a halogen atom.
  • Examples of the diamine residue having the structure represented by the formula (35) include 2,6-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,3 -Diaminotoluene, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 2- Nitro-1,2-phenylenediamine, 3-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 3- Hydroxy-1,5-phenylenediamine, 4-hydroxy-1,5-phenylenediamine, 4-hydroxy-1,2- Derived diamine residue from a diamine compound such Enirenjiamin like.
  • Examples of the tetracarboxylic acid residue in which two or more aromatic rings are bonded by a quaternary carbon atom include 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 4,4′-isopropylpropylene. Redene diphthalic anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3 A tetracarboxylic acid residue derived from a tetracarboxylic dianhydride such as -dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.
  • Examples of the tetracarboxylic acid residue in which two or more aromatic rings are bonded by a hexavalent sulfur atom include, for example, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ', 4'-Diphenylsulfonetetracarboxylic dianhydride, 2,2', 3,3'-diphenylsulfonetetracarboxylic dianhydride, 4,4 '-[p-sulfonylbis (phenylenesulfanyl)] diphthalic acid
  • tetracarboxylic acid residues derived from tetracarboxylic dianhydrides such as anhydrides and 3,3 ′-[p-sulfonylbis (phenylenesulfanyl)] diphthalic anhydride.
  • Examples of the diamine residue in which two or more aromatic rings are bonded by a quaternary carbon atom include 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexa Fluoropropane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminopheny) -2-propyl] benzene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) propane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (2-aminophenyl) Nyl
  • Examples of the diamine residue in which two or more aromatic rings are connected by a hexavalent sulfur atom include, for example, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, and 3,4′-diaminodiphenylsulfone.
  • the weight average molecular weight (Mw) of the polyimide precursor and / or polyimide contained in the composition is not particularly limited, but is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, more preferably, in terms of polystyrene equivalent weight average molecular weight. 10,000 or more. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150,000 or less. By being in this range, the solubility, solution viscosity, composition viscosity, melt viscosity, and the like are in a range that can be easily handled by ordinary production equipment, which is preferable.
  • the polystyrene-reduced weight average molecular weight can be determined by gel permeation chromatography (GPC).
  • the number average molecular weight (Mn) of the polyimide precursor and / or polyimide contained in the composition is not particularly limited, but is usually 500 or more, preferably 1000 or more, more preferably 2500 or more, more preferably, in terms of number average molecular weight in terms of polystyrene. It is 5000 or more. Moreover, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in this range, solubility, solution viscosity, composition viscosity, melt viscosity, and the like are in a range that can be easily handled by ordinary production equipment, which is preferable.
  • the number average molecular weight of the polyimide precursor and / or polyimide can be measured by the same method as the weight average molecular weight.
  • the molecular weight distribution (PDI, (weight average molecular weight / number average molecular weight (Mw / Mn))) of the polyimide precursor and / or polyimide contained in the composition is usually 1 or more, preferably 1.1 or more, more preferably 1 .2 or more, usually 10 or less, preferably 9 or less, more preferably 8 or less.
  • the molecular weight distribution is preferably in this range in that a composition with high uniformity tends to be obtained. Further, in the prevention of whitening of the film, being in the above range tends to obtain a film excellent in uniformity of components in the film, suppression of whitening and smoothness of the film.
  • the molecular weight distribution of a polyimide precursor precursor and / or a polyimide can be calculated
  • the imidation rate of the polyimide precursor contained in a polyimide precursor composition there is no restriction
  • the imidation ratio of the polyimide precursor contained in the polyimide precursor composition can be determined by a conventionally known method such as the NMR method, the IR method, and the titration method.
  • the polyimide precursor and / or polyimide composition of the present invention can contain other components in addition to the polyimide precursor and / or polyimide and solvent described above as long as the effects of the present invention are not impaired.
  • examples of other components include surfactants, solvents, antioxidants, lubricants, colorants, stabilizers, UV absorbers, antistatic agents, flame retardants, plasticizers, mold release agents, leveling agents, and antifoaming agents. Etc.
  • These additive components may be added at any stage of any process for producing a polyimide precursor and / or a polyimide composition.
  • the leveling agent include silicone compounds.
  • the silicone compound is not particularly limited.
  • examples thereof include polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, highly polymerized silicone, amino-modified silicone, amino-derivative silicone, phenyl-modified silicone, and polyether-modified silicone.
  • Reaction which obtains a polyimide precursor from tetracarboxylic dianhydride and a diamine compound can be performed on conventionally known conditions. There are no particular limitations on the order of addition or addition method of the tetracarboxylic dianhydride and the diamine compound.
  • a polyimide precursor can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.
  • the amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride.
  • the concentration of tetracarboxylic dianhydride and diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the polyimide precursor.
  • the total mass% of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably with respect to the total liquid amount. Is 50% by mass or less, more preferably 40% by mass or less.
  • the reaction temperature is not particularly limited as long as the reaction proceeds, but is usually 0 ° C or higher, preferably 20 ° C or higher, and usually 120 ° C or lower, preferably 100 ° C or lower.
  • the reaction time is usually 1 hour or more, preferably 2 hours or more, usually 100 hours or less, preferably 42 hours or less, more preferably 24 hours or less. By performing the reaction under such conditions, a polyimide precursor can be obtained at low cost and high yield.
  • the pressure during the reaction may be normal pressure, increased pressure, or reduced pressure.
  • the atmosphere may be air or an inert atmosphere.
  • the solvent used in this reaction is not particularly limited.
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane
  • Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and fluorobenzene
  • ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene
  • ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomer Gly
  • the obtained polyimide precursor may be used as it is, or may be added to a poor solvent to be precipitated in a solid state and then re-dissolved in another solvent to obtain a polyimide precursor composition.
  • the poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of the polyimide precursor, but an ether solvent such as diethyl ether or diisopropyl ether; a ketone solvent such as acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone; Examples thereof include alcohol solvents such as methanol, ethanol, isopropyl alcohol and the like. Among them, alcohol solvents such as isopropyl alcohol are preferable in that precipitates can be obtained efficiently, the boiling point is low, and drying is easy. These solvents may be used alone or in combination of two or more in any ratio and combination.
  • the solvent for dissolving the polyimide precursor is not particularly limited.
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; N, N-dimethylformamide, N, N-dimethylacetamide
  • Amide solvents such as N-methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate Solvent; and the like.
  • anisole N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether and ethylene glycol monomethyl ether are particularly preferable.
  • These solvents may be used alone or in combination of two or more in any ratio and combination.
  • the composition of the present invention may contain other solvents without departing from the gist of the present invention.
  • the type is not particularly limited, but alcohol is preferred because of good coatability. There is no restriction
  • the vapor pressure at 20 ° C. is not particularly limited, but is preferably 50000 Pa or less, more preferably 20000 Pa or less, further preferably 10,000 Pa or less, and more preferably 5000 Pa or less. Moreover, there is no lower limit, and the lower one is preferable, but it is, for example, 1 Pa or more. When the vapor pressure is within this range, a film excellent in uniformity of the composition and in-film components, whitening suppression, and smoothness tends to be obtained.
  • the boiling point of the alcohol added to the composition is not particularly limited, but is preferably 60 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. Moreover, Preferably it is 300 degrees C or less, More preferably, it is 280 degrees C or less, More preferably, it is 250 degrees C or less. When the boiling point is within this range, the concentration change of the polyimide precursor composition during film formation such as coating is reduced, so that a film excellent in uniformity of components in the film, suppression of whitening and smoothness of the film can be obtained. There is a tendency. Furthermore, the residual solvent in the film after drying or heating tends to decrease.
  • the octanol / water partition coefficient (log ⁇ ) of the alcohol added to the composition is not particularly limited, but is preferably 0 or more, more preferably 0.5 or more, and even more preferably 1 or more. There is no upper limit, and a larger one is preferred. When log ⁇ is within this range, the influence of moisture on the film is reduced, and whitening during film formation tends to be suppressed.
  • the ratio of alcohol added to the composition with respect to the total solvent is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. Moreover, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1.0 mass% or more is further more preferable. By being in this range, the solubility of the polyimide precursor and / or polyimide is increased, and whitening during film formation tends to be suppressed.
  • the alcohol added to the composition is preferably at least one selected from the group consisting of aromatic alcohols, aliphatic alcohols and glycol monoether alcohols. These solvents may be used alone or in combination at any ratio. Especially, since the solubility of a polyimide precursor and / or a polyimide becomes high, an aliphatic alcohol or glycol monoether type alcohol is preferable, and an aliphatic alcohol is especially preferable.
  • the number of carbon atoms is preferably 4 or more, and more preferably 5 or more. Moreover, it is preferable that it is 20 or less, and it is still more preferable that it is 15 or less.
  • the branch position is ⁇ and / or ⁇ .
  • the alcohol added to a composition is not specifically limited, The following are mentioned specifically.
  • aromatic alcohol examples include benzyl alcohol, salicyl alcohol, diphenylmethanol, and vanillyl alcohol.
  • aliphatic alcohol examples include methanol having 1 carbon; ethanol having 2 carbons; 1-propanol and 2-propanol having 3 carbons; 1-butanol, 2-butanol and isobutanol having 4 carbons.
  • glycol monoether alcohol examples include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
  • the resulting film tends to be easily affected by the environment in which the film is formed. is there.
  • the solubility of the composition decreases due to moisture absorption before drying, and a polyimide precursor or polyimide may be deposited, resulting in whitening (whitening) of the film.
  • original polyimide characteristics such as heat resistance and mechanical characteristics cannot be obtained even if drying or heating is performed on a film that has been whitened.
  • the solvent is selected from the group consisting of ether solvents, ketone solvents, amide solvents, sulfone solvents, heterocyclic solvents, phenol solvents, lactone solvents, and ester solvents.
  • a solvent having a vapor pressure at 20 ° C. of 50000 Pa or less hereinafter sometimes referred to as solvent A
  • an alcohol hereinafter sometimes referred to as solvent B
  • the solvent B is preferably at least one selected from the group consisting of aromatic alcohols, aliphatic alcohols, and glycol monoether alcohols. These solvents may be used alone or in combination at any ratio. Especially, since the solubility of a polyimide precursor becomes high, aliphatic alcohol or glycol monoether type
  • the number of carbon atoms is preferably 4 or more, and more preferably 5 or more. Moreover, it is preferable that it is 20 or less, and it is still more preferable that it is 15 or less.
  • the branch position is particularly preferably a ⁇ and / or ⁇ position.
  • the vapor pressure difference between the solvent A and the solvent B is not particularly limited, but is preferably 10,000 Pa or less, more preferably 5000 Pa or less, and still more preferably 1000 Pa or less. There is no lower limit, and the vapor pressure difference may be zero. Further, either the solvent A or the solvent B may have a higher vapor pressure.
  • the concentration change of the polyimide precursor composition during film formation such as coating is reduced. Therefore, it is excellent in whitening suppression, uniformity of components in the film, and film smoothness. A film tends to be obtained. Further, the residual solvent in the film after drying or heating tends to decrease.
  • the difference in boiling point between the solvent A and the solvent B is not particularly limited, but is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 50 ° C. or lower. There is no lower limit, and the boiling point difference may be zero. Further, either of the boiling points of the solvent A and the solvent B may be higher.
  • the difference in boiling point is within a specific range, the concentration change of the polyimide precursor composition during film formation is reduced, and thus a film excellent in whitening suppression, uniformity of components in the film and film smoothness can be obtained. There is a tendency. Further, the residual solvent in the film after drying or heating tends to decrease.
  • the ratio of the ratio of the solvent A and the solvent B to the total solvent is not particularly limited. preferable. Moreover, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1.0 mass% or more is further more preferable. When the ratio of the ratio of the solvent A and the solvent B is within this range, the solubility of the polyimide precursor is maintained and the whitening suppression effect tends to be obtained.
  • the film formed using the above solvent is particularly excellent in transparency and low colorability, it can be suitably used for applications such as coating materials, surface protective layers, adhesives, device substrates and insulating films.
  • the viscosity of the composition of the present invention is not particularly limited, but is usually 200 cP or more, preferably 300 cP or more, more preferably 500 cP or more at a viscosity of 20% at 25 ° C., usually 200000 cP or less, preferably 100000 cP or less, Preferably it is 80,000 cP or less.
  • the viscosity of the composition can be measured by a conventionally known method. For example, a vibration type viscometer, an E type viscometer, or the like can be used.
  • the concentration of the polyimide precursor and / or polyimide contained in the composition of the present invention is not particularly limited, but is usually 3% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, and usually 60%. It is not more than mass%, preferably not more than 50 mass%, more preferably not more than 45 mass%. When the concentration is within this range, the production becomes easy, and the film thickness tends to be uniform during film formation.
  • the concentration of the composition can be measured by a conventionally known method. For example, it can be determined by the method described above.
  • polyimide contained in the composition there is no particular limitation on the method for producing the polyimide contained in the composition.
  • the method of manufacturing a polyimide precursor and obtaining a polyimide the method of manufacturing a polyimide directly from tetracarboxylic dianhydride and a diamine compound, etc. can be used.
  • a polyimide can be obtained by dehydrating and cyclizing the polyimide precursor obtained by the above method in the presence of a solvent.
  • imidation can be performed using any conventionally known method, for example, thermal imidization for thermal cyclization, chemical imidization for chemical cyclization, and the like can be given. These imidation reactions may be performed alone or in combination.
  • Examples of the solvent for imidizing the polyimide precursor include the same solvents as those used in the reaction for obtaining the polyimide precursor.
  • the solvent at the time of manufacturing the polyimide precursor and the solvent at the time of manufacturing the polyimide may be the same or different.
  • water generated by imidization may be discharged out of the system in order to inhibit the ring closure reaction.
  • the concentration of the polyimide precursor during the imidation reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. By carrying out in this range, the production efficiency tends to be high and the solution viscosity tends to be easy to produce.
  • the imidation reaction temperature is not particularly limited, but is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. Performing in this range is preferable because the imidization reaction proceeds efficiently and reactions other than the imidization reaction tend to be suppressed.
  • the pressure during the reaction may be normal pressure, pressurization, or reduced pressure.
  • the atmosphere may be air or an inert atmosphere.
  • a compound having a function of enhancing nucleophilicity and electrophilicity can be added.
  • tertiary amine compounds or heterocyclic compounds are preferable, and triethylamine, imidazole, or pyridine is more preferable because it tends to control the imidation rate.
  • These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
  • the amount of the imidization accelerator used is usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 1 mol% or more based on the carboxyl group or ester group. Moreover, it is preferable that it is 50 mol% or less, and it is more preferable that it is 10 mol% or less.
  • the usage-amount of a catalyst exists in such a range, it exists in the tendency for the imidation reaction to advance efficiently and to obtain the polyimide which controlled the imidation ratio.
  • the timing which adds an imidation promoter can be adjusted suitably in order to make it a desired imidation rate, may be before a heating start, and may be during a heating. Moreover, you may add in multiple times.
  • a polyimide can be obtained by chemically imidizing a polyimide precursor using a dehydration condensing agent in the presence of a solvent.
  • a solvent used in the chemical imidization include the same solvents as those used in the reaction for obtaining the polyimide precursor.
  • dehydrating condensing agent examples include N, N-2-substituted carbodiimides such as N, N-dicyclohexylcarbodiimide and N, N-diphenylcarbodiimide; acid anhydrides such as acetic anhydride and trifluoroacetic anhydride; thionyl chloride and tosyl chloride and the like.
  • acid anhydrides and halogenated compounds are preferable, and in particular, acid anhydrides tend to allow the imidization reaction to proceed efficiently and to obtain a polyimide with a controlled imidization rate.
  • acid anhydrides tend to allow the imidization reaction to proceed efficiently and to obtain a polyimide with a controlled imidization rate.
  • These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
  • the amount of these dehydrating condensing agents to be used is usually 0.1 mol or more, preferably 0.2 mol or more, usually 1.0 mol or less, preferably 0.9 mol or less with respect to 1 mol of the polyimide precursor.
  • the imidation rate can be controlled, production efficiency tends to be high, and the solution viscosity tends to be easy to manufacture.
  • the imidation reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and is usually 150 ° C. or lower, preferably 130 ° C. or lower, more preferably 100 ° C. or lower. It is preferable to carry out in this range since the imidization reaction proceeds efficiently and a polyimide having a controlled imidization rate tends to be obtained. Furthermore, it is preferable because side reactions other than the imidization reaction are suppressed.
  • the pressure during the reaction may be normal pressure, increased pressure, or reduced pressure.
  • the atmosphere may be air or an inert atmosphere.
  • the above-mentioned tertiary amines can be added in the same manner as in the heating imidization.
  • a polyimide can be directly obtained from a tetracarboxylic dianhydride and a diamine compound using a conventionally known method. This method performs imidization from synthesis of a poimide precursor to imidization without stopping the reaction or isolating the precursor.
  • tetracarboxylic dianhydride and diamine compound there are no particular limitations on the order and method of addition of tetracarboxylic dianhydride and diamine compound.
  • the temperature at which the reaction until imidization proceeds by sequentially adding tetracarboxylic dianhydride and diamine compound to the solvent.
  • the polyimide is obtained by stirring at.
  • the amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride.
  • the concentration of tetracarboxylic dianhydride and diamine compound in the solvent can be set as appropriate for each condition and viscosity during polymerization, but the total mass of tetracarboxylic dianhydride and diamine compound is a special setting. However, it is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less, based on the total liquid amount. When the concentration in the solvent is within an appropriate range, elongation of molecular weight tends to occur, and stirring tends to be facilitated.
  • Examples of the solvent used in this reaction include the same solvents as those used in the reaction for obtaining the polyimide precursor. Moreover, also when obtaining a polyimide from a tetracarboxylic dianhydride and a diamine compound, heating imidation and / or chemical imidation can be used similarly to the case where a polyimide is obtained from a polyimide precursor.
  • the reaction conditions for heating imidization and chemical imidization in this case are the same as described above.
  • the obtained polyimide may be used as it is as a polyimide composition, or may be added to a poor solvent to precipitate the polyimide in a solid state, and then re-dissolved in another solvent to be used as a polyimide composition. it can.
  • the poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of polyimide.
  • ether solvents such as diethyl ether and diisopropyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, and the like.
  • alcohol solvents such as isopropyl alcohol are preferable because precipitates can be obtained efficiently and the boiling point is low and the drying tends to be easy.
  • These solvents may be used alone or in combination of two or more in any ratio and combination.
  • Examples of the solvent for re-dissolving polyimide include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, and anisole; N, N-dimethylformamide, N, N-dimethylacetamide, N An amide solvent such as methyl-2-pyrrolidone; an aprotic solvent such as dimethyl sulfoxide; a glycol solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; Etc.
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, and anisole
  • N N-dimethylformamide
  • N N-dimethylace
  • anisole N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether, and ethylene glycol monomethyl ether are particularly preferable.
  • These solvents may be used alone or in combination of two or more in any ratio and combination.
  • composition of the present invention may contain other solvents without departing from the gist of the present invention.
  • the type is not particularly limited, but alcohol is preferred because of good coatability. Preferred alcohols are the same as those described above.
  • a coupling agent such as a silane coupling agent or a titanium coupling agent can be added in order to adjust the adhesion to the coated body.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltripropoxysilane, ⁇ -aminopropyltributoxysilane, ⁇ -aminoethyltriethoxysilane, ⁇ -Aminoethyltrimethoxysilane, ⁇ -aminoethyltripropoxysilane, ⁇ -aminoethyltributoxysilane, ⁇ -aminobutyltriethoxysilane, ⁇ -aminobutyltrimethoxysilane, ⁇ -aminobutyltripropoxysilane, ⁇ -amino Examples include butyltributoxysilane.
  • titanium coupling agent examples include ⁇ -aminopropyltriethoxytitanium, ⁇ -aminopropyltrimethoxytitanium, ⁇ -aminopropyltripropoxytitanium, ⁇ -aminopropyltributoxytitanium, ⁇ -aminoethyltriethoxytitanium, ⁇ -Aminoethyltrimethoxytitanium, ⁇ -aminoethyltripropoxytitanium, ⁇ -aminoethyltributoxytitanium, ⁇ -aminobutyltriethoxytitanium, ⁇ -aminobutyltrimethoxytitanium, ⁇ -aminobutyltripropoxytitanium, ⁇ -amino Examples thereof include butyl tributoxy titanium.
  • These coupling agents may be used singly or in combination of two or more in any ratio and combination.
  • the amount used at this time is preferably 0.1% by mass or more and 3% by mass or less with respect to the polyimide.
  • additives can be blended as necessary.
  • other powdery, granular, plate-like, fiber-like inorganic fillers and organic fillers can be blended within a range not impairing the effects of the present invention.
  • fillers may be processed into a flat shape such as a non-woven fabric or may be used in combination.
  • various additives commonly used in resin compositions such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers, mold release agents, etc. Can be blended. These various fillers and additive components may be added at any stage of any process for producing polyimide.
  • the polyimide according to the present invention contains a tetracarboxylic acid residue and a diamine residue, and has a partial structure selected from group III and one or more partial groups selected from group IV as a tetracarboxylic acid residue.
  • the diamine residue has a partial structure represented by the formula (11).
  • X 1 represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group.
  • n ′ and m ′ each independently represent 0 or 1
  • R 5 and R 6 each independently represents an alkyl group, an alkenyl group or an aromatic ring.
  • R 5 and R 6 may be different or the same, and may form a ring.
  • Y ′ represents a direct bond or a divalent organic group.
  • R 7 and R 8 each independently represents an alkyl group, an alkoxy group, an amino group or a hydroxyl group.
  • X 1 in formula (7) has the same meaning as X in formula (1), and the preferred range and the substituent that may be present are also synonymous.
  • N ′ and m ′ in the formula (9) have the same meanings as n and m in the formula (3), respectively, and a preferable range is also the same.
  • R ⁇ 5 > and R ⁇ 6 > are synonymous with R ⁇ 1 > and R ⁇ 2 > of Formula (3), respectively, A preferable range and the substituent which may have are also synonymous.
  • Y ′ in formula (10) has the same meaning as Y in formula (4), and the preferred range and the substituent that may be present are also synonymous.
  • R 7 and R 8 in the formula (11) have the same meanings as R 3 and R 4 in the formula (5), respectively, and the preferred range and the substituents that may be included are also the same.
  • the polyimide of the present invention has a tetracarboxylic acid residue having a structure other than the partial structure represented by the above formula (7), formula (8), formula (9) and formula (10) without departing from the gist of the present invention. You may have. Moreover, you may have the diamine residue which has other than the partial structure shown by Formula (11). Examples of the tetracarboxylic acid residue having other than the partial structure represented by the above formula (7), formula (8), formula (9) and formula (10) include the above formula (1), formula (2) and formula (3).
  • tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides, shown as tetracarboxylic acid residues having other than the partial structure represented by formula (4) And tetracarboxylic acid residues derived from.
  • diamine residue having other than the partial structure represented by the above formula (11) a diamine residue derived from a diamine compound represented as a diamine residue having other than the partial structure represented by the above formula (5) Can be mentioned.
  • the polyimide of the present invention preferably has a tetracarboxylic acid residue and / or a diamine residue having a bent portion, since it tends to improve optical properties.
  • a tetracarboxylic acid and / or diamine residue having a bent portion the tetracarboxylic acid and / or diamine residue having a bent portion which may be included in the polyimide precursor and / or polyimide in the composition of the present invention. It is synonymous with group, and its preferable range is also synonymous.
  • diamine residues having other than the partial structure represented by formula (11) it is preferable to have a diamine residue having a partial structure represented by formula (12) in order to improve optical properties.
  • Z ′ represents a direct bond, a sulfonyl group, an alkylene group, a carbonyl group or an ether bond
  • a ′ and B ′ each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group.
  • Z ′, A ′, and B ′ in the formula (12) have the same meanings as Z, A, and B in the formula (6), respectively, and the preferred ranges and the substituents that may be included are also the same.
  • the partial structure contained in the polyimide can be obtained by analyzing the composition of the raw material monomer by solid-state NMR, IR, or the like. Further, after dissolution with alkali, it can be determined by gas chromatography (GC), 1 H-NMR, 13 C-NMR, two-dimensional NMR, mass spectrometry, and the like.
  • GC gas chromatography
  • the shape of the polyimide of the present invention is not particularly limited, but can take various forms such as powder, pellets, and films.
  • the polyimide of the present invention is preferably soluble in a solvent.
  • Soluble in a solvent is as defined above, and the solvent used is also synonymous.
  • Polyimide properties The properties and properties of the polyimide of the present invention are not particularly limited without departing from the gist of the present invention.
  • the tensile strength of the polyimide of the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, usually 400 MPa or less, preferably 300 MPa or less.
  • the tensile elastic modulus is not particularly limited, but is usually 1000 MPa or more, preferably 1500 MPa or more, and usually 20 GPa or less, preferably 10 GPa or less.
  • the tensile elongation is not particularly limited, but is usually 5% GL or more, preferably 10% GL or more, more preferably 20 GL% or more, and usually 300% GL or less, preferably 200 GL% or less. By being in the range as described above, there is strength, which is particularly useful when a film is used.
  • These tensile strength, tensile elastic modulus, and tensile elongation can be determined, for example, by measuring film-like polyimide with a tensile tester.
  • the glass transition temperature of the polyimide of the present invention is not particularly limited, but is usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher. When the glass transition temperature is within this range, heat resistance can be obtained.
  • the glass transition temperature can be measured by using, for example, differential scanning calorimetry, viscoelasticity measurement, thermogravimetric / differential thermal simultaneous analysis, and the like.
  • the linear expansion coefficient of the polyimide of the present invention is usually 60 ppm / K or less, preferably 50 ppm / K or less, more preferably 45 ppm / K or less, still more preferably 40 ppm / K, particularly preferably in the range of 100 ° C. to 150 ° C. 30 ppm / K or less.
  • This range is preferable because, for example, when a device using polyimide as a film is produced, the dimensional stability is high, and it is difficult for members such as electronic elements and color filters to break and deform.
  • the measuring method is not specifically limited, For example, it can measure by the method of an Example using a film-like polyimide.
  • the transmittance of the polyimide of the present invention is a film, and when the film thickness is 1 to 100 ⁇ m, the transmittance with respect to a light beam of 500 nm is usually 55% or more, preferably 60% or more, more preferably 70% or more. By being in this range, the light emission efficiency of the device can be used effectively.
  • the transmittance can be measured by the method described in JIS K 7361-1 (1997).
  • the retardation is a wavelength to be used, for example, an arbitrary wavelength between 400 and 800 nm for device use, and the retardation in the thickness direction of the film (Rth) is usually 300 nm or less, Preferably it is 200 nm or less, More preferably, it is 170 nm or less, More preferably, it is 150 nm or less, More preferably, it is 140 nm or less, Most preferably, it is 120 nm or less.
  • the in-plane retardation (R0) of the film is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and even more preferably 1 nm or less. This range is preferable because the visibility of the device is improved.
  • the polyimide of the present invention is useful for film applications. In addition to film applications, it can be applied to a wide range of applications. For example, it can be used for production of a flexible solar cell member, a display member, a liquid crystal display carrier, a heat-resistant insulating tape, a heat-resistant adhesive tape, a capacitor or a film for a flexible printed circuit board. Further, for example, it can be used for manufacturing a structural member reinforced with glass fiber or carbon fiber, a small coil bobbin, or a molded product of a terminal insulating tube.
  • laminated materials such as insulating spacers, magnetic head spacers or transformer spacers.
  • enamel coating materials such as electric wire / cable insulation coating materials, low-temperature storage tanks, space insulation materials, and integrated circuits.
  • heat-resistant yarns woven fabrics or nonwoven fabrics.
  • the present invention is a polyimide film containing a tetracarboxylic acid residue and a diamine residue, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bent portion, and the linear expansion coefficient is 60 ppm / It is related also to the polyimide film characterized by being below K and retardation being below 200 nm.
  • the definition of the bending part which at least any one of a tetracarboxylic acid residue and a diamine residue has is the same as that of the bending part mentioned above, and its preferable structure is also the same.
  • the linear expansion coefficient of the polyimide film may be 60 ppm / K or less, preferably 50 ppm / K or less, more preferably 45 ppm / K or less, still more preferably 40 ppm / K, and particularly preferably 30 ppm / K or less.
  • the measuring method is not specifically limited, For example, it can measure by the method of an Example using a film-like polyimide.
  • the method of setting the linear expansion coefficient of the polyimide film to 60 ppm / K or less is not particularly limited.
  • the linear expansion coefficient of a polyimide film can be made in the said range by performing the method of extending
  • the filler and the like are not particularly limited, and examples thereof include inorganic fillers such as powder, granule, plate, and fiber, or organic fillers.
  • inorganic fillers include oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice and pumice balloon; hydroxides such as aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate; calcium carbonate Carbonates such as magnesium carbonate, dolomite, and dawsonite; sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, and calcium sulfite; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate Silicates such as carbon fiber, carbon black, graphite and carbon hollow spheres; powders of molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate, boron fiber, etc.
  • oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice and pumice balloon
  • hydroxides such as
  • examples of the organic filler include carbon nanotubes, fullerenes, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, polypropylene fibers, thermosetting resin powders, and rubbers.
  • a filler what processed into flat form, such as a nonwoven fabric, may be used, and several materials may be mixed and used. The linear expansion coefficient can be measured by a thermomechanical device.
  • the retardation of the polyimide film may be 200 nm or less, preferably 170 nm or less, more preferably 150 nm or less, still more preferably 140 nm or less, and particularly preferably 120 nm or less.
  • the in-plane retardation (R0) of the film is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and even more preferably 1 nm or less. This range is preferable because the visibility of the device is improved.
  • the method of setting the retardation of the polyimide film to 200 nm or less is not particularly limited.
  • a method using a composition containing at least one of the polyimide precursor and polyimide, a method of mixing a compound having a negative retardation, or a resin The retardation of a polyimide film can be made into the said range by using the method etc. which form into a film using the base material which has a linear expansion coefficient equivalent to a polyimide.
  • the compound or resin having negative retardation is not particularly limited, and examples thereof include a styrene compound, an acrylic compound, a styrene resin, and an acrylic resin.
  • Examples of the base material having a linear expansion coefficient equivalent to that of polyimide include a metal foil and a resin substrate. Retardation can be measured by a retardation film / optical material inspection apparatus or the like.
  • the transmittance of the polyimide film of the present invention is usually 55% or more, preferably 60% or more, more preferably 70% or more with respect to a light beam of 500 nm. By being in this range, the light emission efficiency of the device can be used effectively.
  • the transmittance can be measured by the method described in JIS K 7361-1 (1997).
  • the yellowness (yellow index: YI) at a film thickness of 10 ⁇ m is usually ⁇ 10 or more, preferably ⁇ 5 or more, more preferably ⁇ 1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less. By being in this range, when polyimide is used as a device member, the efficiency of light emission can be used effectively.
  • the yellow index can be measured by using, for example, a spectral color meter.
  • the thickness of the polyimide film is not particularly limited, but is usually 1 ⁇ m or more, preferably 2 ⁇ m or more, and is usually 200 ⁇ m or less, preferably 100 ⁇ m or less. When the film has an appropriate thickness, sufficient resistance can be maintained and the flexible device can be thinned.
  • a substrate made of glass such as float glass or soda glass, or a plastic such as polyethylene terephthalate, polycarbonate, or polyolefin can be used.
  • a functional silane-containing compound or a functional titanium-containing compound can be prefaced on the surface of the substrate. Further, ultraviolet treatment, plasma treatment, or the like can be performed.
  • the method for volatilizing the solvent of the polyimide precursor and / or the polyimide composition is not particularly limited.
  • the solvent is volatilized by heating the applied material to be coated and / or by volatilizing the solvent under reduced pressure.
  • the heating method is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, heating by contact using a hot plate or a hot roll, and the like.
  • the heating temperature for volatilizing the solvent can be a suitable temperature depending on the type of the solvent, but is usually 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher, more preferably 60 ° C. or higher. It is. Moreover, it is 400 degrees C or less normally, Preferably it is 380 degrees C or less, More preferably, it is 350 degrees C or less, More preferably, it is 300 degrees C or less.
  • the temperature is equal to or higher than the above lower limit, the residual solvent can be reduced and the film can be sufficiently dried. Moreover, by being below the said upper limit, the bubble etc. which generate
  • the heating atmosphere may be either air or an inert atmosphere, and is not particularly limited. However, if the polyimide film is required to be colorless and transparent, it can be heated under an inert atmosphere such as nitrogen to suppress coloring. preferable.
  • the method for peeling the polyimide film formed on the carrier by coating and drying is not particularly limited, and examples thereof include laser peeling, mechanical peeling, and peeling by immersion in water or hot water.
  • a method for melting and molding the polyimide precursor resin and / or polyimide resin for example, an injection molding method, an extrusion molding method, a hollow molding method.
  • the present invention will be described in more detail with reference to examples and comparative examples.
  • the following examples are shown in order to describe the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.
  • the values of various conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above upper limit or lower limit value. It may be a range defined by a combination of values of the examples or values between the examples.
  • Example 1 In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer, 5.7 g (0.019 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3, 2.6 g (0.009 mol) of 3 ′, 4,4′-bicyclohexanetetracarboxylic dianhydride (H-BPDA), 1.4 g (0.006 mol) of pyromellitic anhydride (PMDA), 2,2 5.6 g (0.018 mol) of '-bis (trifluoromethyl) benzidine (6F-m-TB), 4.3 g (0.018 mol) of 4,4'-diaminodiphenylsulfone, N-methyl-2-pyrrolidone ( NMP) 73 g was added. The mixture was heated while stirring and reacted at 80 ° C. for 6 hours to obtain
  • composition 1 was applied on a glass substrate using a 100 ⁇ m applicator and heated at 350 ° C. for 30 minutes to obtain a polyimide film 1 having a thickness of 10 ⁇ m.
  • CTE linear expansion coefficient
  • the retardation (Rth) value in the thickness direction of the film 1 was measured and calculated using a measurement retardation film / optical material inspection apparatus ("RETS100" manufactured by Otsuka Electronics Co., Ltd.). The measurement results are shown in Table 2.
  • the retardation (Rth) value in the thickness direction of the film used this time is a value at a wavelength of 460 nm and a film thickness of 10 ⁇ m.
  • the yellow index (YI) value of the polyimide film 1 was measured using SM color computer SM5 manufactured by Suga Test Instruments Co., Ltd.
  • the YI value used this time is a value calculated as a YI value per 10 ⁇ m of film thickness.
  • Example 2 In Example 1, BPAD was 1.7 g (0.006 mol), H-BPDA was 1.8 g (0.006 mol), PMDA was 3.9 g (0.018 mol), and 6F-m-TB was 5.5 g (0 0.017 mol), polyimide precursor composition 2 and polyimide film 2 were prepared in the same manner as in Example 1 except that 3.2 g (0.013 mol) of 4,4′-diaminodiphenylsulfone and NMP were changed to 65 g. Obtained. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 3 5.3 g (0.018 mol) of BPDA of Example 1, 2.5 g (0.008 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 7.9 g of 0F-m-TB (0 0.025 mol), 4,4′-diaminodiphenylsulfone was changed to 2.0 g (0.008 mol), and NMP was changed to 71 g, and polyimide precursor composition 3 and polyimide film 3 were prepared in the same manner as in Example 1. Obtained. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 4 5.4 g (0.018 mol) of BPDA of Example 1, 2.5 g (0.008 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 9.5 g of 6F-m-TB (0 0.03 mol), 4,4′-diaminodiphenyl sulfone was changed to 0.8 g (0.003 mol), and NMP was changed to 78 g to obtain a polyimide precursor composition 4 and a polyimide film 4 in the same manner as in Example 1. It was. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 5 A four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer was charged with 4.9 g (0.017 mol) of BPDA, 2.3 g (0.007 mol) of H-BPDA, and PMDA1. 0.2 g (0.006 mol), 6F-m-TB 8.6 g (0.027 mol), 4,4′-diaminodiphenylsulfone 0.7 g (0.003 mol), NMP 71 g, and toluene 14 g were added. The mixture was heated to reflux at 200 ° C. for 13 hours with stirring to obtain a polyimide composition 5.
  • Example 6 4.1 g (0.014 mol) of BPDA of Example 1, 2.1 g (0.007 mol) of H-BPDA, 1.9 g (0.009 mol) of PMDA, and 8.4 g of 0F-m-TB (0 .026 mol), 2.2 g (0.009 mol) of 4,4′-diaminodiphenylsulfone and NMP of 82 g were changed to 1.9 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride.
  • a polyimide precursor composition 6 and a polyimide film 6 were obtained in the same manner as in Example 1 except that (0.005 mol) was added. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 7 5.4 g (0.018 mol) of BPDA of Example 6, 1.2 g (0.004 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 3,3 ′, 4,4′-diphenyl 1.5 g (0.004 mol) of sulfonetetracarboxylic dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 2.0 g (0.008 mol) of 4,4′-diaminodiphenylsulfone, A polyimide precursor composition 7 and a polyimide film 7 were obtained in the same manner as in Example 6 except that NMP was changed to 78 g. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 8 5.4 g (0.018 mol) of BPDA of Example 6, 2.0 g (0.007 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 3,3 ′, 4,4′-diphenyl 0.6 g (0.002 mol) of sulfonetetracarboxylic dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 2.0 g (0.008 mol) of 4,4′-diaminodiphenylsulfone,
  • a polyimide precursor composition 8 and a polyimide film 8 were obtained in the same manner as in Example 6 except that NMP was changed to 77 g.
  • CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 9 In Example 6, 5.9 g (0.019 mol) of BPDA, 1.9 g (0.006 mol) of H-BPDA, 1.4 g (0.006 mol) of PMDA, 7.7 g of 0F-m-TB (0 .024 mol), 4,4′-diaminodiphenylsulfone 1.2 g (0.005 mol), NMP 76 g, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 9, A polyimide precursor composition 9 and a polyimide film 9 were obtained in the same manner as in Example 6 except that the amount was changed to 1.1 g (0.003 mol) of 9-bis (4-aminophenyl) fluorene. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 10 9.8 g (0.033 mol) of BPDA of Example 6, 2.3 g (0.007 mol) of H-BPDA, 2.4 g (0.011 mol) of PMDA, and 18.0 g (0 of 0) of F-m-TB 0.056 mol), 4.7 g (0.019 mol) of 4,4′-diaminodiphenylsulfone, and 141 g of NMP, and 2,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride was changed to 2, The same as Example 6 except that the amount was changed to 9.9 g (0.022 mol) of 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.
  • the polyimide precursor composition 10 and the polyimide film 10 were obtained by the method. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results
  • Example 11 3.8 g (0.013 mol) of BPDA of Example 10, 2.0 g (0.007 mol) of H-BPDA, 1.7 g (0.008 mol) of PMDA, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2.1 g (0.005 mol), 6F-m-TB 7.9 g (0.025 mol), 4,4 A polyimide precursor composition 11 and a polyimide film 11 were obtained in the same manner as in Example 10, except that 2.0 g (0.008 mol) of '-diaminodiphenylsulfone and 79 g of NMP were changed. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 12 Example 10 except that BPDA of Example 10 was changed to 6.6 g (0.022 mol), H-BPDA was changed to 2.2 g (0.007 mol), PMDA was changed to 4.9 g (0.022 mol), and NMP was changed to 139 g.
  • the polyimide precursor composition 12 and the polyimide film 12 were obtained by the same method. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 13 5.2 g (0.018 mol) of BPDA of Example 9, 1.8 g (0.006 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 6.2 g of 6F-m-TB (0 .020 mol), 1.9 g (0.008 mol) of 4,4′-diaminodiphenylsulfone, 53 g of NMP, and 9,9-bis (4-aminophenyl) fluorene with 2,2-bis (3- A polyimide precursor composition 13 and a polyimide film 13 were obtained in the same manner as in Example 9 except that 1.1 g (0.003 mol) of amino-4-hydroxyphenyl) -hexafluoropropane was used. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 14 The BPAD of Example 1 was 6.6 g (0.022 mol), H-BPDA was 3.0 g (0.010 mol), PMDA was 1.6 g (0.007 mol), and 6F-m-TB was 9.6 g (0 .030 mol), NMP was changed to 73 g, and 4,4′-diaminodiphenyl sulfone was changed to 3.4 g (0.010 mol) of 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene.
  • a polyimide precursor composition 14 and a polyimide film 14 were obtained by the same method as in Example 1 except that. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 15 Except that 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene of Example 14 was changed to 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene A polyimide precursor composition 14 and a polyimide film 14 were obtained by the same method as in Example 13. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 2 A polyimide film 18 was obtained from the obtained composition 18 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Comparative Example 8 Comparative Example 7 and Comparative Example 7 except that 6.8 g (0.022 mol) of H-BPDA, 5.9 g (0.023 mol) of 4,4′-diaminodiphenylsulfone, and DMAc were changed to 37 g of NMP.
  • the polyimide precursor composition 24 and the polyimide film 24 were obtained by the same method. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • Example 2 CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
  • the ratio of the tetracarboxylic dianhydride to the diamine compound was adjusted so that the viscosity of the composition in the raw material was 200 to 600 cP, whereby a composition 27 was obtained. The ratio is shown in Table 3.
  • the composition 27 was applied on a glass substrate and heated. When the obtained film was peeled off, cracks occurred and the film could not be obtained.
  • the ratio of the tetracarboxylic dianhydride to the raw material diamine compound used in Example 7 was adjusted so that the viscosity of the composition was 200 to 600 cP, whereby a composition 28 was obtained.
  • the ratio is shown in Table 3.
  • the composition 28 was applied on a glass substrate and heated. The obtained film did not crack and could be peeled off.
  • the polyimide films 1 to 15 of the present invention have both a low linear expansion coefficient and a low retardation.
  • the polyimide film shown in the comparative example cannot achieve both a low linear expansion coefficient and a low retardation.
  • the composition 28 containing the bent portion could be formed into a film even when the viscosity was reduced to 200 to 600 cP, but the composition containing no bent portion was not included. 27, it was difficult to form a film when the viscosity was lowered. Therefore, it was shown that the composition can be obtained in a wide viscosity range by having a bent portion and can be applied to various coating methods. It was.
  • the polyimide precursor composition of the present invention can be used for coating materials, surface protective layers, adhesives, device substrates, insulating films and the like.

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Abstract

The purpose of the present invention is to provide a polyimide material which exhibits excellent heat resistance and transmissivity, a low coefficient of linear expansion, and low retardation. The present invention pertains to a polyimide film containing a tetracarboxylic acid residue and a diamine residue, and characterized in that the tetracarboxylic acid residue and/or the diamine residue has a curved section, the coefficient of linear expansion is 60 ppm/K or less, and the retardation is 200nm or less.

Description

ポリイミド前駆体及び／又はポリイミドを含む組成物、並びにポリイミドフィルムComposition containing polyimide precursor and / or polyimide, and polyimide film
　本発明は、特定の部分構造を有するポリイミド前駆体及び／又はポリイミド組成物、膜を形成する際の、膜の白化を抑制するポリイミド前駆体組成物、特定の部分構造を有し、耐熱性、透過率、低線膨張係数及び低リタデーションに優れたポリイミド並びにポリイミドフィルムに関する。 The present invention includes a polyimide precursor and / or a polyimide composition having a specific partial structure, a polyimide precursor composition that suppresses whitening of the film when forming a film, a specific partial structure, heat resistance, The present invention relates to a polyimide and a polyimide film excellent in transmittance, low linear expansion coefficient and low retardation.
　近年、電気、電子部品、輸送機器、宇宙及び航空機等の分野において、デバイスの薄型化や軽量化、さらにはフレキシブル化が要求されるようになってきた。これらのデバイスには、ガラス基板上に薄型トランジスタや透明電極等の電子素子が形成されているが、このガラス基板をプラスチック材料に変えることにより、パネル自体のフレキシブル化、薄型化、軽量化が図られる。 In recent years, in the fields of electric, electronic parts, transportation equipment, space, aircraft, etc., there has been a demand for thinner and lighter devices and more flexible devices. In these devices, electronic elements such as thin transistors and transparent electrodes are formed on a glass substrate. By changing this glass substrate to a plastic material, the panel itself can be made flexible, thin, and lightweight. It is done.
　このようなデバイスの製造工程では、高温となる工程があるため、デバイス用基板には高い耐熱性が求められる。そこで、高耐熱プラスチックの一つとしてポリイミド材料の開発が行われている。また、デバイス用基板は加熱工程等における寸法変化が大きいと、電子素子やカラーフィルター等の部材の破断、変形等の原因となり、品質安定性が悪くなってしまう。
　また、耐熱性の他に、電気絶縁性、耐摩耗性、耐薬品性及び機械特性等に優れたポリイミド材料の開発が行われている。 In such a device manufacturing process, there is a process that becomes high temperature, and thus a high heat resistance is required for the device substrate. Therefore, development of polyimide materials as one of high heat-resistant plastics has been performed. In addition, when the dimensional change in the heating process or the like is large in the device substrate, it causes breakage and deformation of members such as electronic elements and color filters, and the quality stability is deteriorated.
In addition to heat resistance, polyimide materials that are excellent in electrical insulation, wear resistance, chemical resistance, mechanical properties, and the like have been developed.
　特許文献１では、耐熱性を有し、寸法変化の少ない（線膨張係数の小さい）ポリイミド材料が挙げられている。また、特許文献２ではアミド結合を有するアミドイミド材料が提案されている。 Patent Document 1 mentions a polyimide material having heat resistance and little dimensional change (small linear expansion coefficient). Patent Document 2 proposes an amideimide material having an amide bond.
日本国特開２０１２－１４４６０３号公報Japanese Unexamined Patent Publication No. 2012-144603 日本国特開２０１３－０２８６８８号公報Japanese Unexamined Patent Publication No. 2013-028688
　しかし、特許文献１で提案されているように、ポリイミドを構成するモノマーが芳香族化合物のみの場合、面内配向が強くなりリタデーションが高く、位相差を生じてしまう。このような位相差を生じる材料を用いると、例えばディスプレイの正面や斜め方向の視野性が悪くなってしまう傾向にある。
　また、特許文献２で提案されたアミドイミド材料のようにアミド結合を有する場合、アミド結合は、吸水性、溶媒親和性が高いため、得られるポリイミド樹脂の加水分解性が高くなってしまう傾向にある。
　以上のように、デバイス用材料に適用するために必要な特性である、耐熱性、透過率、低線膨張係数、及び低リタデーションを同時に満たす材料は提案されていない。 However, as proposed in Patent Document 1, when the monomer constituting the polyimide is only an aromatic compound, the in-plane orientation is strong, the retardation is high, and a phase difference is generated. If a material that generates such a phase difference is used, for example, the front view of the display or the visual field in an oblique direction tends to deteriorate.
Moreover, when it has an amide bond like the amide imide material proposed by patent document 2, since an amide bond has high water absorption and solvent affinity, it exists in the tendency for the hydrolyzability of the polyimide resin obtained to become high. .
As described above, no material has been proposed that simultaneously satisfies heat resistance, transmittance, low linear expansion coefficient, and low retardation, which are characteristics necessary for application to device materials.
　本発明は、前記課題を鑑みて成し遂げられたものであり、耐熱性、透過率、低線膨張係数及び低リタデーションに優れたポリイミド材料を提供することにある。 The present invention has been accomplished in view of the above problems, and is to provide a polyimide material excellent in heat resistance, transmittance, low linear expansion coefficient and low retardation.
　本発明は以下の構成を有するものである。
［１］テトラカルボン酸残基及びジアミン残基を含むポリイミドフィルムであって、前記テトラカルボン酸残基及びジアミン残基の少なくともいずれか一方が屈曲部位を有し、線膨張係数が６０ｐｐｍ／Ｋ以下であり、かつ、リタデーションが２００ｎｍ以下であることを特徴とするポリイミドフィルム。
［２］フィルムの膜厚が１０μｍの際のイエローインデックスが、－１０以上、２０以下である、前記［１］に記載のポリイミドフィルム。
［３］ポリイミド前駆体及びポリイミドの少なくともいずれか一方を含む組成物であって、前記ポリイミド前駆体及びポリイミドは、テトラカルボン酸残基及びジアミン残基を含み、前記テトラカルボン酸残基が下記式（１’）で表される部分構造、下記式（２）で表される部分構造及び下記式（４’）で表される部分構造を有し、前記ジアミン残基が下記式（５）で表される部分構造を有し、更に、前記テトラカルボン酸残基及びジアミン残基の少なくともいずれか一方が屈曲部位を有することを特徴とする組成物。 The present invention has the following configuration.
[1] A polyimide film containing a tetracarboxylic acid residue and a diamine residue, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bent portion, and the linear expansion coefficient is 60 ppm / K or less And the retardation is 200 nm or less, The polyimide film characterized by the above-mentioned.
[2] The polyimide film according to [1], wherein the yellow index when the film thickness is 10 μm is −10 or more and 20 or less.
[3] A composition containing at least one of a polyimide precursor and a polyimide, wherein the polyimide precursor and polyimide contain a tetracarboxylic acid residue and a diamine residue, and the tetracarboxylic acid residue is represented by the following formula: A partial structure represented by (1 ′), a partial structure represented by the following formula (2), and a partial structure represented by the following formula (4 ′), wherein the diamine residue is represented by the following formula (5): A composition having a partial structure represented, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bent portion.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ただし式中の記号は以下の意味を表す。
　Ｘ２は直接結合、２級若しくは３級炭素原子を有する結合、またはエーテル結合である。
　Ｒ３及びＲ４はそれぞれ独立して、アルキル基、アルコキシ基、アミノ基及び水酸基からなる群より選ばれる官能基である。 However, the symbol in a formula represents the following meaning.
X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
R 3 and R 4 are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
［４］前記テトラカルボン酸残基中の前記式（４’）で表される部分構造を有するテトラカルボン酸残基の割合が、２ｍｏｌ％以上、９５ｍｏｌ％以下である、前記［３］に記載の組成物。
［５］前記テトラカルボン酸残基中の前記式（１’）で表される部分構造を有するテトラカルボン酸残基及び前記式（２）で表される部分構造を有するテトラカルボン酸残基の和の割合が、５ｍｏｌ％以上、９５ｍｏｌ％以下である、前記［３］又は［４］に記載の組成物。
［６］前記テトラカルボン酸残基及びジアミン残基の和に対する、前記屈曲部位の割合が、０．１ｍｏｌ％以上、１５０ｍｏｌ％以下である、前記［３］乃至［５］の何れか１に記載の組成物。 [4] The ratio of the tetracarboxylic acid residue having the partial structure represented by the formula (4 ′) in the tetracarboxylic acid residue is 2 mol% or more and 95 mol% or less. Composition.
[5] A tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) and a tetracarboxylic acid residue having a partial structure represented by the formula (2) in the tetracarboxylic acid residue. The composition according to the above [3] or [4], wherein the sum ratio is 5 mol% or more and 95 mol% or less.
[6] The method according to any one of [3] to [5], wherein a ratio of the bent portion to a sum of the tetracarboxylic acid residue and the diamine residue is 0.1 mol% or more and 150 mol% or less. Composition.
　本発明によれば、耐熱性、透過率、低線膨張係数及び低リタデーションに優れた、ポリイミド前駆体及び／又はポリイミド組成物、ポリイミド並びにポリイミドフィルムを提供することができる。 According to the present invention, it is possible to provide a polyimide precursor and / or a polyimide composition, a polyimide and a polyimide film which are excellent in heat resistance, transmittance, low linear expansion coefficient and low retardation.
　以下に、本発明の実施の形態を詳細に説明するが、以下に例示する物や方法等は、本発明の実施態様の一例（代表例）であり、本発明はその要旨を逸脱しない限り、これらの内容に限定されない。
　ここで、“重量％”と“質量％”とは同義である。 Embodiments of the present invention will be described in detail below, but the objects and methods exemplified below are examples (representative examples) of embodiments of the present invention, and the present invention is not deviated from the gist thereof. It is not limited to these contents.
Here, “weight%” and “mass%” are synonymous.
［組成物］
　本発明の組成物は、ポリイミド前駆体及びポリイミドの少なくともいずれか一方を含む組成物であって、前記ポリイミド前駆体及び／又はポリイミドは、テトラカルボン酸残基とジアミン残基を含み、前記テトラカルボン酸残基は、下記に示すＩ群から１つ以上選択される部分構造と下記に示すＩＩ群から１つ以上選択される部分構造とを有し、前記ジアミン残基は、下記式（５）で表される部分構造を有することを特徴とする組成物である。 [Composition]
The composition of the present invention is a composition containing at least one of a polyimide precursor and a polyimide, and the polyimide precursor and / or polyimide contains a tetracarboxylic acid residue and a diamine residue, and the tetracarboxylic acid The acid residue has a partial structure selected from one or more from group I shown below and a partial structure selected from one or more from group II shown below, wherein the diamine residue is represented by the following formula (5): It is a composition characterized by having the partial structure represented by these.
　ただし式中の記号は以下の意味を表す。
　Ｘは直接結合、アルキレン基、カルボニル基、エーテル結合又はスルホニル基を示す。
　ｎ及びｍは、それぞれ独立して、０又は１を示す。
　Ｒ１及びＲ２は、それぞれ独立して、アルキレン基、アルケニレン基又は芳香環を示す。Ｒ１及びＲ２は互いに結合して環を形成していてもよい。
　Ｙは、直接結合又は２価の有機基を示す。
　Ｒ３及びＲ４は、それぞれ独立して、アルキル基、アルコキシ基、アミノ基又は水酸基を示す。 However, the symbol in a formula represents the following meaning.
X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group.
n and m each independently represent 0 or 1.
R 1 and R 2 each independently represents an alkylene group, an alkenylene group or an aromatic ring. R 1 and R 2 may be bonded to each other to form a ring.
Y represents a direct bond or a divalent organic group.
R 3 and R 4 each independently represents an alkyl group, an alkoxy group, an amino group or a hydroxyl group.
　テトラカルボン酸残基として、Ｉ群から１つ以上選択される部分構造及びＩＩ群から１つ以上選択される部分構造を有し、ジアミン残基として、式（５）で表される部分構造を有することで、本願発明の効果を奏する理由としては以下が推測される。
　Ｉ群から選択されるテトラカルボン酸残基と、式（５）で表されるジアミン残基を有することで、耐熱性及び機械特性の向上、並びに線膨張係数を下げる効果が得られる。しかし、芳香環化合物のみであると、前記のように、面内配向が強くなりリタデーションが高くなる傾向となるが、ＩＩ群から選択されるテトラカルボン酸残基を有することで、これらの効果を得ながらも、リタデーションを制御することが可能となる。また、ＩＩ群から選択されるテトラカルボン酸残基を有することで、さらに高い透過率が得られ、加えて低屈折率、有機溶媒に対する溶解性、成型体の可撓性向上の効果も得られると推測される。
　なお、本発明において、テトラカルボン酸残基とは、テトラカルボン酸二無水物から誘導された、四価の基のことを表す。また、本発明において、ジアミン残基とは、ジアミン化合物又はジイソシアネート化合物から誘導された、２価の基のことを表す。 The tetracarboxylic acid residue has a partial structure selected from one or more from group I and a partial structure selected from one or more from group II, and the diamine residue has a partial structure represented by formula (5) The following is estimated as a reason for having the effect of the present invention.
By having the tetracarboxylic acid residue selected from Group I and the diamine residue represented by the formula (5), the effects of improving heat resistance and mechanical properties and lowering the linear expansion coefficient can be obtained. However, when only the aromatic ring compound is used, as described above, the in-plane orientation tends to be strong and the retardation tends to be high, but by having a tetracarboxylic acid residue selected from Group II, these effects can be achieved. It is possible to control retardation while obtaining. Further, by having a tetracarboxylic acid residue selected from Group II, higher transmittance can be obtained, and in addition, the effects of improving the flexibility of the molded product can be obtained with a low refractive index, solubility in organic solvents. It is guessed.
In the present invention, the tetracarboxylic acid residue represents a tetravalent group derived from tetracarboxylic dianhydride. Moreover, in this invention, a diamine residue represents the bivalent group induced | guided | derived from the diamine compound or the diisocyanate compound.
　本発明にかかる組成物において、前記Ｉ群から選択される部分構造が下記式（１’）で表される部分構造及び式（２）で表される部分構造であり、前記ＩＩ群から選択される部分構造が下記式（４’）で表される部分構造であり、ジアミン残基の部分構造が下記式（５）で表される部分構造であることが線膨張係数と光学特性のバランスを取りやすいため好ましく、さらにテトラカルボン酸残基及びジアミン残基の少なくとも一方が屈曲部位を有することがさらに好ましい。
　各部分構造および屈曲部位の詳細については後述する。 In the composition according to the present invention, the partial structure selected from the group I is a partial structure represented by the following formula (1 ′) and a partial structure represented by the formula (2), and is selected from the group II The partial structure represented by the following formula (4 ′) and the partial structure of the diamine residue being the partial structure represented by the following formula (5) balance the linear expansion coefficient and the optical characteristics. It is preferable because it is easy to remove, and it is more preferable that at least one of the tetracarboxylic acid residue and the diamine residue has a bending site.
Details of each partial structure and bending portion will be described later.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　ただし式中の記号は以下の意味を表す。
　Ｘ２は直接結合、２級若しくは３級炭素原子を有する結合、またはエーテル結合である。
　Ｒ３及びＲ４はそれぞれ独立して、アルキル基、アルコキシ基、アミノ基及び水酸基からなる群より選ばれる官能基である。 However, the symbol in a formula represents the following meaning.
X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
R 3 and R 4 are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
　本発明の組成物は、前記ポリイミド前駆体及び／又はポリイミド以外にも他の成分を含んでいてもよい。例えば、成膜の際にイミド化率をさらに上げるために、イミド化剤を添加することができる。 The composition of the present invention may contain other components in addition to the polyimide precursor and / or polyimide. For example, an imidizing agent can be added in order to further increase the imidization rate during film formation.
［組成物に含まれるポリイミド前駆体及び／又はポリイミド］
　本発明に係る組成物に含まれるポリイミド前駆体及び／又はポリイミドは、テトラカルボン酸残基とジアミン残基を含むものである。前記テトラカルボン酸残基としてＩ群から１つ以上選択される部分構造及びＩＩ群から１つ以上選択される部分構造を有し、前記ジアミン残基として、式（５）で表される部分構造を有するものであれば特に限定されない。また、これらは溶媒に可溶な化合物であることが好ましい。
　本発明の組成物は、ポリイミド前駆体及び／又はポリイミドとして、テトラカルボン酸残基としてＩ群及びＩＩ群の部分構造を有さないものを有していてもよい。また、ジアミン残基として式（５）で表される部分構造を有さないものを有していてもよい。 [Polyimide precursor and / or polyimide contained in composition]
The polyimide precursor and / or polyimide contained in the composition according to the present invention includes a tetracarboxylic acid residue and a diamine residue. The tetracarboxylic acid residue has a partial structure selected from one or more groups from group I and a partial structure selected from one or more groups from group II. The partial structure represented by formula (5) as the diamine residue If it has, it will not specifically limit. These are preferably compounds soluble in a solvent.
The composition of the present invention may have a polyimide precursor and / or a polyimide that does not have a partial structure of Group I or Group II as a tetracarboxylic acid residue. Moreover, you may have what does not have the partial structure represented by Formula (5) as a diamine residue.
　本発明において、「溶媒に可溶」とは、組成物を構成する溶媒中で、ポリイミド前駆体及び／又はポリイミドを室温（２５℃）において、０．５質量％で溶解させた場合に完溶することをいう。
　完溶する濃度としては通常０．５質量％以上であり、好ましくは１質量％以上、より好ましくは１０質量％以上である。
　組成物を構成する溶媒とは、後述する本発明の組成物に含まれるポリイミド前駆体及びポリイミドを得る際に用いる溶媒、再沈させる際に用いる溶媒等が挙げられる。 In the present invention, “soluble in a solvent” means complete dissolution when a polyimide precursor and / or polyimide is dissolved at 0.5% by mass at room temperature (25 ° C.) in a solvent constituting the composition. To do.
The concentration for complete dissolution is usually 0.5% by mass or more, preferably 1% by mass or more, and more preferably 10% by mass or more.
Examples of the solvent constituting the composition include a solvent used for obtaining a polyimide precursor and polyimide contained in the composition of the present invention described later, a solvent used for reprecipitation, and the like.
　組成物中のポリイミド前駆体及び／又はポリイミドの濃度は、従来知られている方法を用いて適宜確認することができる。例えば、組成物の溶媒を、減圧乾燥等の方法を用いて留去し、留去する前後の質量比から求めることができる。
　組成物の濃度が０．５質量％より薄い場合は、溶媒の減圧留去等の方法を用いて、組成物を濃縮し、溶媒に可溶か否かを判断することができる。組成物の濃度が濃い場合は、組成物の溶媒を用いて希釈することによって、濃度を０．５質量％とすることができる。また組成物の溶媒が不明の場合は、例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド系溶媒；ジメチルスルホキシド等の非プロトン系溶媒；アニソール、クレゾール、キシレン、トルエン等の芳香族系溶媒、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系溶媒等を用いて希釈することができる。 The concentration of the polyimide precursor and / or polyimide in the composition can be appropriately confirmed using a conventionally known method. For example, the solvent of the composition can be obtained by distillation using a method such as drying under reduced pressure, and the mass ratio before and after the distillation.
When the concentration of the composition is less than 0.5% by mass, the composition can be concentrated using a method such as distilling off the solvent under reduced pressure to determine whether or not the composition is soluble in the solvent. When the concentration of the composition is high, the concentration can be made 0.5 mass% by diluting with the solvent of the composition. When the solvent of the composition is unknown, for example, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; anisole It can be diluted with aromatic solvents such as cresol, xylene and toluene, glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate. .
　テトラカルボン酸残基として、Ｉ群及びＩＩ群の部分構造が挙げられる。テトラカルボン酸残基として、Ｉ群から１つ以上選択される部分構造及びＩＩ群から１つ以上選択される部分構造を有すれば特に限定はなく、例えば、Ｉ群から複数の部分構造を有していてもよく、式（１）で表される部分構造を複数有していてもよい。
　Ｉ群の中では、線膨張係数を低くする効果が高いため、式（１）で表される部分構造を有することが好ましく、式（１）で表される部分構造と式（２）で表される部分構造を両方有することが、耐熱性の向上、機械特性の向上及び線膨張係数を下げる効果が得られる傾向となるためさらに好ましい。
　また、ＩＩ群の中では、光学特性が向上するため式（４）で表される部分構造を有することが好ましい。 Examples of the tetracarboxylic acid residue include partial structures of Group I and Group II. The tetracarboxylic acid residue is not particularly limited as long as it has a partial structure selected from one or more groups from group I and a partial structure selected from one or more groups from group II. For example, it has a plurality of partial structures from group I. And may have a plurality of partial structures represented by the formula (1).
In the group I, since the effect of lowering the linear expansion coefficient is high, it preferably has a partial structure represented by the formula (1), and is represented by the partial structure represented by the formula (1) and the formula (2). It is more preferable to have both of the partial structures to be obtained because the heat resistance, the mechanical properties, and the linear expansion coefficient tend to be obtained.
Further, in the group II, it is preferable to have a partial structure represented by the formula (4) in order to improve optical characteristics.
　本発明の組成物に含まれるテトラカルボン酸残基の内、Ｉ群及びＩＩ群の各群から選択される部分構造を有するテトラカルボン酸残基が占める割合は、特に制限はないが、通常１０ｍｏｌ％以上、好ましくは３０ｍｏｌ％以上、より好ましくは５０ｍｏｌ％以上である。この範囲にあることで、光学特性が良好で、線膨張係数の低い、ポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 The ratio of the tetracarboxylic acid residues having a partial structure selected from each group of Group I and Group II among tetracarboxylic acid residues contained in the composition of the present invention is not particularly limited, but is usually 10 mol. % Or more, preferably 30 mol% or more, more preferably 50 mol% or more. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
　Ｉ群から選択される部分構造を有するテトラカルボン酸残基とＩＩ群から選択される部分を有するテトラカルボン酸残基との割合は、特に制限はない。
　本発明の組成物に含まれるテトラカルボン酸残基の内、Ｉ群から選択される部分構造を有するテトラカルボン酸残基が占める割合は、通常５ｍｏｌ％以上、好ましくは１０ｍｏｌ％以上、より好ましくは１５ｍｏｌ％以上、通常９５ｍｏｌ％以下、好ましくは９０ｍｏｌ％以下、より好ましくは８５ｍｏｌ％以下である。この範囲にあることで、光学特性が良好で、線膨張係数の低いポリイミド前駆体及び／又はポリイミド組成物を得ることができる。
　Ｉ群から選択される部分構造を有するテトラカルボン酸残基とＩＩ群から選択される部分構造を有するテトラカルボン酸残基の比率は特に制限はないが、ＩＩ群のＩ群に対する割合で、通常５ｍｏｌ％以上、好ましくは１０ｍｏｌ％以上、より好ましくは１５ｍｏｌ％以上であり、通常５００ｍｏｌ％以下、好ましくは３００ｍｏｌ％以下、より好ましくは２００ｍｏｌ％以下、さらに好ましくは１５０ｍｏｌ％以下である。 The ratio of the tetracarboxylic acid residue having a partial structure selected from Group I and the tetracarboxylic acid residue having a moiety selected from Group II is not particularly limited.
Of the tetracarboxylic acid residues contained in the composition of the present invention, the proportion of the tetracarboxylic acid residues having a partial structure selected from Group I is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
The ratio of the tetracarboxylic acid residue having a partial structure selected from Group I and the tetracarboxylic acid residue having a partial structure selected from Group II is not particularly limited. It is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and is usually 500 mol% or less, preferably 300 mol% or less, more preferably 200 mol% or less, and even more preferably 150 mol% or less.
　本発明の組成物に含まれるテトラカルボン酸残基の内、式（１’）で表される部分構造を有するテトラカルボン酸残基、式（２）で表される部分構造を有するテトラカルボン酸残基及び式（４’）で表される部分構造を有するテトラカルボン酸残基が占める和の割合は、特に制限はないが、通常１０ｍｏｌ％以上、好ましくは３０ｍｏｌ％以上、より好ましくは５０ｍｏｌ％以上である。この範囲にあることで、光学特性が良好で、線膨張係数の低い、ポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 Among the tetracarboxylic acid residues contained in the composition of the present invention, a tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) and a tetracarboxylic acid having a partial structure represented by the formula (2) The ratio of the sum of the residue and the tetracarboxylic acid residue having the partial structure represented by the formula (4 ′) is not particularly limited, but is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol%. That's it. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
　式（１’）で表される部分構造を有するテトラカルボン酸残基及び式（２）で表される部分構造を有するテトラカルボン酸残基と式（４’）で表される部分構造を有するテトラカルボン酸残基との割合は、特に制限はない。
　本発明の組成物に含まれるテトラカルボン酸残基の内、式（１’）で表される部分構造を有するテトラカルボン酸残基及び式（２）で表される部分構造を有するテトラカルボン酸残基が占める和の割合は、通常５ｍｏｌ％以上、好ましくは１０ｍｏｌ％以上、より好ましくは１５ｍｏｌ％以上、通常９５ｍｏｌ％以下、好ましくは９０ｍｏｌ％以下、より好ましくは８５ｍｏｌ％以下である。この範囲にあることで、光学特性が良好で、線膨張係数の低いポリイミド前駆体及び／又はポリイミド組成物を得ることができる。また、該組成物から得られるポリイミドフイルムにおいて、レーザー加工に用いられる３０８ｎｍ、３５５ｎｍ付近の吸収が増加し、レーザー加工に対応可能となり得る。 A tetracarboxylic acid residue having a partial structure represented by the formula (1 ′), a tetracarboxylic acid residue having a partial structure represented by the formula (2), and a partial structure represented by the formula (4 ′) The ratio with the tetracarboxylic acid residue is not particularly limited.
Among the tetracarboxylic acid residues contained in the composition of the present invention, a tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) and a tetracarboxylic acid having a partial structure represented by the formula (2) The ratio of the sum occupied by the residues is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient. Moreover, in the polyimide film obtained from the composition, the absorption near 308 nm and 355 nm used for laser processing increases, and it can be compatible with laser processing.
　式（１’）で表される部分構造を有するテトラカルボン酸残基及び式（２）で表される部分構造を有するテトラカルボン酸残基と式（４’）で表される部分構造を有するテトラカルボン酸残基との比率は特に制限はないが、式（１’）で表される部分構造を有するテトラカルボン酸残基及び式（２）で表される部分構造を有するテトラカルボン酸残基の和に対する式（４’）で表される部分構造を有するテトラカルボン酸残基の割合で、通常５ｍｏｌ％以上、好ましくは１０ｍｏｌ％以上、より好ましくは１５ｍｏｌ％以上であり、通常５００ｍｏｌ％以下、好ましくは３００ｍｏｌ％以下、より好ましくは２００ｍｏｌ％以下、さらに好ましくは１５０ｍｏｌ％以下である。この範囲にあることで、光学特性が良好で、線膨張係数の低いポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 A tetracarboxylic acid residue having a partial structure represented by the formula (1 ′), a tetracarboxylic acid residue having a partial structure represented by the formula (2), and a partial structure represented by the formula (4 ′) The ratio with the tetracarboxylic acid residue is not particularly limited, but the tetracarboxylic acid residue having the partial structure represented by the formula (1 ′) and the tetracarboxylic acid residue having the partial structure represented by the formula (2) The proportion of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) relative to the sum of the groups, is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 500 mol% or less. , Preferably 300 mol% or less, more preferably 200 mol% or less, and even more preferably 150 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
　本発明の組成物に含まれるテトラカルボン酸残基の内、式（４’）で表される部分構造を有するテトラカルボン酸残基が占める割合は、通常２ｍｏｌ％以上、好ましくは５ｍｏｌ％以上、より好ましくは８ｍｏｌ％以上、通常９５ｍｏｌ％以下、好ましくは９０ｍｏｌ％以下、より好ましくは８５ｍｏｌ％以下である。この範囲にあることで、光学特性が良好で、線膨張係数の低いポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 The proportion of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) in the tetracarboxylic acid residue contained in the composition of the present invention is usually 2 mol% or more, preferably 5 mol% or more, More preferably, it is 8 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
　式（１’）で表される部分構造を有するテトラカルボン酸残基に対する、式（２）で表される部分構造を有するテトラカルボン酸残基の比は特に制限はないが、通常０．５ｍｏｌ％以上、好ましくは１ｍｏｌ％以上、より好ましくは３ｍｏｌ％以上であり、通常５００ｍｏｌ％以下、好ましくは４００ｍｏｌ％以下、より好ましくは３００ｍｏｌ％以下である。この範囲にあることで、光学特性が良好で、線膨張係数の低いポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 The ratio of the tetracarboxylic acid residue having a partial structure represented by the formula (2) to the tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) is not particularly limited, but is usually 0.5 mol. % Or more, preferably 1 mol% or more, more preferably 3 mol% or more, and usually 500 mol% or less, preferably 400 mol% or less, more preferably 300 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
　式（２）で表される部分構造を有するテトラカルボン酸残基中の式（１’）で表される部分構造を有するテトラカルボン酸残基及び式（２）で表される部分構造を有するテトラカルボン酸残基の和に対する割合は特に制限はないが、通常１ｍｏｌ％以上、好ましくは３ｍｏｌ％以上、より好ましくは５ｍｏｌ％以上であり、通常９５ｍｏｌ％以下、好ましくは９０ｍｏｌ％以下、より好ましくは８５ｍｏｌ％以下である。この範囲にあることで、光学特性が良好で、線膨張係数の低いポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 A tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) in a tetracarboxylic acid residue having a partial structure represented by the formula (2) and a partial structure represented by the formula (2) The ratio of the tetracarboxylic acid residue to the sum is not particularly limited, but is usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually 95 mol% or less, preferably 90 mol% or less, more preferably It is 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
　テトラカルボン酸残基の割合は、ＮＭＲ、固体ＮＭＲ、ＩＲ等によって原料モノマーの組成を解析することにより求めることができる。また、アルカリで溶解した後に、ガスクロマトグラフィー（ＧＣ）、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、二次元ＮＭＲ及び質量分析等によって求めることができる。 The ratio of the tetracarboxylic acid residue can be determined by analyzing the composition of the raw material monomer by NMR, solid NMR, IR, or the like. Further, after dissolution with alkali, it can be determined by gas chromatography (GC), 1 H-NMR, 13 C-NMR, two-dimensional NMR, mass spectrometry, and the like.
　ジアミン残基中に占める式（５）で表される部分構造を有するジアミン残基の割合は、特に制限はないが、通常０．１ｍｏｌ％以上、好ましくは１ｍｏｌ％以上、より好ましくは５ｍｏｌ％以上、さらに好ましくは７ｍｏｌ％以上、さらに好ましくは２０ｍｏｌ％以上、さらに好ましくは３０ｍｏｌ％以上、さらに好ましくは４０ｍｏｌ％以上、さらに好ましくは５０ｍｏｌ％以上である。また、特に上限はなく１００ｍｏｌ％でもよい。ジアミン残基中に占める式（５）で表される部分構造を有するジアミン残基を特定量以上含むことで、線膨張係数の低いポリイミドを得るためのポリイミド前駆体及び／又はポリイミド組成物を得ることができる。 The ratio of the diamine residue having a partial structure represented by the formula (5) in the diamine residue is not particularly limited, but is usually 0.1 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more. More preferably, it is 7 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol% or more. Moreover, there is no upper limit in particular and 100 mol% may be sufficient. A polyimide precursor and / or a polyimide composition for obtaining a polyimide having a low linear expansion coefficient is obtained by including a specific amount or more of the diamine residue having the partial structure represented by the formula (5) in the diamine residue. be able to.
　ジアミン残基を誘導するジアミン化合物の量は、テトラカルボン酸二無水物１ｍｏｌに対して、通常０．７ｍｏｌ以上、好ましくは０．８ｍｏｌ以上であり、通常１．３ｍｏｌ以下、好ましくは１．２ｍｏｌ以下である。ジアミン化合物の量をこの範囲とすることにより、分子量が適正な範囲のポリイミド前駆体及び／又はポリイミドを得ることができる。 The amount of the diamine compound for inducing the diamine residue is usually 0.7 mol or more, preferably 0.8 mol or more, usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. It is. By setting the amount of the diamine compound within this range, a polyimide precursor and / or a polyimide having an appropriate molecular weight can be obtained.
（Ｉ群及びＩＩ群）
Ｉ群：下記式（１）及び式（２）を示す。 (Group I and Group II)
Group I: The following formulas (1) and (2) are shown.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
［式（１）において、
Ｘは直接結合、アルキレン基、カルボニル基、エーテル結合又はスルホニル基を示す。］ [In Formula (1),
X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. ]
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
ＩＩ群：下記式（３）及び式（４）を示す。 Group II: The following formulas (3) and (4) are shown.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
［式（３）において、
ｎ、ｍは、それぞれ独立に、０又は１を示し、
Ｒ１及びＲ２は、それぞれ独立に、アルキレン基、アルケニレン基又は芳香環を示す。
Ｒ１及びＲ２は、異なっていても同じでもよく、また環を形成していてよい。］ [In Formula (3),
n and m each independently represent 0 or 1,
R 1 and R 2 each independently represents an alkylene group, an alkenylene group or an aromatic ring.
R 1 and R 2 may be different or the same, and may form a ring. ]
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
［式（４）において、
Ｙは、直接結合又は２価の有機基を示す。］ [In Formula (4),
Y represents a direct bond or a divalent organic group. ]
（Ｉ群）
（式（１）で表される部分構造を有するテトラカルボン酸残基）
　式（１）において、Ｘは、直接結合、アルキレン基、カルボニル基、エーテル結合又はスルホニル基を示す。前記の中でも、線膨張係数を低くする効果が高いため、Ｘは直接結合、カルボニル基又はスルホニル基が好ましく、直接結合がより好ましい。 (Group I)
(Tetracarboxylic acid residue having a partial structure represented by formula (1))
In the formula (1), X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. Among these, X is preferably a direct bond, a carbonyl group or a sulfonyl group, and more preferably a direct bond, since the effect of lowering the linear expansion coefficient is high.
　前記アルキレン基としては、特に限定されないが、炭素数１以上であることが好ましく、２以上がさらに好ましい。一方、８以下が好ましく、５以下が更に好ましい。また、前記アルキレン基は置換基を有していてもよく、例えば、アミノ基、ヒドロキシル基、ハロゲン原子等が挙げられる。 The alkylene group is not particularly limited, but preferably has 1 or more carbon atoms, more preferably 2 or more. On the other hand, it is preferably 8 or less, and more preferably 5 or less. Moreover, the said alkylene group may have a substituent, for example, an amino group, a hydroxyl group, a halogen atom, etc. are mentioned.
　式（１）で表される部分構造を有するテトラカルボン酸残基は特に限定されないが、例えば、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物等のＸが直接結合であるテトラカルボン酸二無水物；ビス（３，４－ジカルボキシフェニル）メタン二無水物、ビス（２，３－ジカルボキシフェニル）メタン二無水物、２，３，３’，４’－テトラカルボキシフェニルメタン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－（２，３，３’，４’－テトラカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）１，１，１，３，３，３－ヘキサフルオロプロパン二無水物等のＸがアルキレン基であるテトラカルボン酸二無水物；３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、２，２’，３，３’－ベンゾフェノンテトラカルボン酸二無水物、２，３，３’，４’－ベンゾフェノンテトラカルボン酸二無水物等のＸがカルボニル基であるテトラカルボン酸二無水物；４，４’－オキシジフタル酸無水物、３，４’－オキシジフタル酸無水物、３，３’－オキシジフタル酸無水物等のＸがエーテル結合であるテトラカルボン酸二無水物；３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、２，３，３’，４’－ジフェニルスルホンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルスルホンテトラカルボン酸二無水物等のＸがスルホニル基であるテトラカルボン酸二無水物；等のテトラカルボン酸二無水物から誘導されるテトラカルボン酸残基が挙げられる。 The tetracarboxylic acid residue having a partial structure represented by the formula (1) is not particularly limited. For example, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, Tetracarboxylic dianhydrides in which X is a direct bond such as 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride; bis (3,4-di Carboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,3,3 ′, 4′-tetracarboxyphenylmethane dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2- (2,3,3 ', 4'-tetracarboxyphenyl) propane Anhydride, 2, A tetracarboxylic dianhydride in which X is an alkylene group, such as bis (3,4-dicarboxyphenyl) 1,1,1,3,3,3-hexafluoropropane dianhydride; 3,3 ′, 4 , 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, etc. Is a carbonyl group; tetracarboxylic acid dianhydride; 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, etc. Carboxylic dianhydride; 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, , 3'-diphenylsulfone tetracarboxylic dianhydride X is tetracarboxylic dianhydride is sulfonyl group; tetracarboxylic acid residue and the like which are derived from tetracarboxylic dianhydride such.
　テトラカルボン酸残基の式（１）で表される部分構造は、下記式（１’）で表される部分構造であることが、耐熱性及び機械特性の向上、並びに線膨張係数を下げる効果が得られる傾向にあるため好ましい。 The partial structure represented by the formula (1) of the tetracarboxylic acid residue is the partial structure represented by the following formula (1 ′), which improves the heat resistance and mechanical properties and lowers the linear expansion coefficient. Is preferable because it tends to be obtained.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（１’）においてＸ２は直接結合、２級若しくは３級炭素原子を有する結合、またはエーテル結合であり、中でも、直接結合が機械特性が向上するため好ましい。また、該組成物から得られるポリイミドフィルムにおいて、レーザー加工に用いられる３０８ｎｍ、３５５ｎｍ付近の吸収が増加し、レーザー加工に対応可能となり得るため好ましい。
　２級又は３級炭素原子を有する結合とは、Ｘ２が炭素数１の２級又は３級炭素原子であることを表す。Ｘ２の炭素原子は、式（１’）中のベンゼン環に連結している以外には水素原子及び/又は置換基に連結している。Ｘ２の炭素原子に連結している置換基として、ハロゲン原子、シアノ基、ニトロ基、スルホ基等が挙げられる。 In formula (1 ′), X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond, and among these, a direct bond is preferable because mechanical properties are improved. Moreover, in the polyimide film obtained from the composition, absorption near 308 nm and 355 nm used for laser processing is increased, which is preferable because it can be applied to laser processing.
The bond having a secondary or tertiary carbon atom means that X 2 is a secondary or tertiary carbon atom having 1 carbon atom. The carbon atom of X 2 is linked to a hydrogen atom and / or a substituent other than being linked to the benzene ring in formula (1 ′). Examples of the substituent connected to the carbon atom of X 2 include a halogen atom, a cyano group, a nitro group, and a sulfo group.
（式（２）で表される部分構造を有するテトラカルボン酸残基）
　式（２）で表される部分構造を有するテトラカルボン酸残基を誘導するテトラカルボン酸二無水物は、ピロメリット酸二無水物等が挙げられる。 (Tetracarboxylic acid residue having a partial structure represented by formula (2))
Examples of the tetracarboxylic dianhydride that derives a tetracarboxylic acid residue having a partial structure represented by the formula (2) include pyromellitic dianhydride.
（ＩＩ群）
（式（３）で表される部分構造を有するテトラカルボン酸残基）
　式（３）において、ｎ及びｍは、それぞれ独立に、０又は１を示す。特に限定されないが、イミド化の反応性の点から、ｎ又はｍの少なくとも一方が１であることが好ましい。Ｒ１及びＲ２は、それぞれ独立に、アルキル基、アルケニル基又は芳香環を示す。Ｒ１及びＲ２は、異なっていても同じでもよく、環を形成していてもよい。また、アルキル基、アルケニル基及び芳香環は、置換基を有していてもよい。
　アルキル基及びアルケニル基としては、それぞれ独立に、炭素数１以上が好ましい。一方、１０以下が好ましく、８以下が更に好ましい。この範囲であることで、有機溶媒への溶解性が高くなる傾向にある。
　芳香環としては、単環及び縮合環のどちらでもよい。具体的にはベンゼン環、ナフタレン環、アントラセン環等が挙げられる。特に有機溶媒への溶解性が高くなる傾向にあるため、ベンゼン環が好ましい。 (Group II)
(Tetracarboxylic acid residue having a partial structure represented by formula (3))
In Formula (3), n and m each independently represent 0 or 1. Although not particularly limited, at least one of n and m is preferably 1 from the viewpoint of imidization reactivity. R 1 and R 2 each independently represents an alkyl group, an alkenyl group or an aromatic ring. R 1 and R 2 may be different or the same, and may form a ring. Moreover, the alkyl group, the alkenyl group, and the aromatic ring may have a substituent.
As an alkyl group and an alkenyl group, C1 or more is preferable each independently. On the other hand, 10 or less is preferable, and 8 or less is more preferable. By being in this range, the solubility in an organic solvent tends to increase.
The aromatic ring may be either a single ring or a condensed ring. Specifically, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned. In particular, a benzene ring is preferable because the solubility in an organic solvent tends to be high.
　式（３）で表される部分構造を有するテトラカルボン酸残基は、特に限定されないが、例えば、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、１，２，３，４－シクロヘキサンテトラカルボン酸二無水物、ビシクロ［２，２，２］オクト－７－エン－２，３，４，６－テトラカルボン酸二無水物、トリシクロ［６，４，０，０２，７］ドデカン－１，８：２，７－テトラカルボン酸二無水物、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、４－（２，５－ジオキソテトラヒドロフラン－３－イル）－１，２，３，４－テトラヒドロナフタレン－１，２－ジカルボン酸無水物等のテトラカルボン酸二無水物から誘導されるテトラカルボン酸残基が挙げられる。 The tetracarboxylic acid residue having a partial structure represented by the formula (3) is not particularly limited. For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct -7-ene-2,3,4,6-tetracarboxylic dianhydride, tricyclo [6,4,0,0 2,7 ] dodecane-1,8: 2,7-tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-di Tetracarboxylic acid residue and the like which are derived from tetracarboxylic dianhydride such as carboxylic acid anhydride.
（式（４）で表される部分構造を有するテトラカルボン酸残基）
　Ｙは、直接結合又は２価の有機基を示す。２価の有機基としては特に限定されないが、例えば、アルキレン基、カルボニル基、エーテル結合、スルホニル基等が挙げられる。この中でも、Ｙは、光学特性が向上する傾向にあるため、直接結合が好ましい。
　前記アルキレン基は、式（１）のＸのアルキレン基の好ましい範囲と同義であり、有していてもよい置換基も同義である。 (Tetracarboxylic acid residue having a partial structure represented by formula (4))
Y represents a direct bond or a divalent organic group. Although it does not specifically limit as a bivalent organic group, For example, an alkylene group, a carbonyl group, an ether bond, a sulfonyl group etc. are mentioned. Among these, Y has a tendency to improve optical characteristics, and therefore, direct bonding is preferable.
The said alkylene group is synonymous with the preferable range of the alkylene group of X of Formula (1), and the substituent which you may have is also synonymous.
　式（４）で表される部分構造を有するテトラカルボン酸残基は、特に限定されないが、例えば、ビシクロヘキサン－３，３’，４，４’－テトラカルボン酸二無水物、ビシクロヘキサン－２，３，３’，４’－テトラカルボン酸二無水物、ビシクロヘキサン－２，２’，３，３’－テトラカルボン酸二無水物等のテトラカルボン酸二無水物から誘導されるテトラカルボン酸残基等が挙げられる。
　これらの中でも光学特性が向上する傾向にあるため、ビシクロヘキサン－３，３’，４，４’－テトラカルボン酸二無水物から誘導されるテトラカルボン酸残基が好ましい。 The tetracarboxylic acid residue having a partial structure represented by the formula (4) is not particularly limited. For example, bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride, bicyclohexane-2 , 3,3 ′, 4′-tetracarboxylic dianhydride, tetracarboxylic dianhydrides such as bicyclohexane-2,2 ′, 3,3′-tetracarboxylic dianhydride Examples include residues.
Among these, a tetracarboxylic acid residue derived from bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride is preferable because optical properties tend to be improved.
　テトラカルボン酸残基の式（４）で表される部分構造は、下記式（４’）で表される部分構造であることで、光学特性が向上するため好ましい。 The partial structure represented by the formula (4) of the tetracarboxylic acid residue is preferably a partial structure represented by the following formula (4 ') because the optical properties are improved.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（ジアミン残基）
　ジアミン残基として、式（５）で表される部分構造が挙げられる。 (Diamine residue)
Examples of the diamine residue include a partial structure represented by the formula (5).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
［式（５）において、Ｒ３及びＲ４は、それぞれ独立に、アルキル基、アルコキシ基、アミノ基又は水酸基を示す。］ [In Formula (5), R < 3 > and R < 4 > shows an alkyl group, an alkoxy group, an amino group, or a hydroxyl group each independently. ]
（式（５）で表される部分構造を有するジアミン残基）
　Ｒ３及びＲ４は、それぞれ独立に、アルキル基、アルコキシ基、アミノ基又は水酸基を示す。
　アルキル基及びアルコキシ基は、それぞれ独立に、炭素数１以上が好ましい。一方、１０以下が好ましく、８以下が更に好ましく、６以下が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にあるため好ましい。
　また、アルキル基及びアルコキシ基は、それぞれ置換基を有していてもよい。アルキル基が有していてもよい置換基としては、ハロゲン原子、シアノ基、ニトロ基、スルホ基等が挙げられる。これらの中でもハロゲン原子を有することが好ましく、フッ素原子が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にある。
　アルコキシ基が有していてもよい置換基としては、炭素数１以上、６以下のアルキル基、ハロゲン原子、シアノ基、ニトロ基、スルホ基、アリル基等が挙げられる。
　この中でも、Ｒ３及びＲ４は光学特性と線膨張係数が向上するため、アルキル基又はアルコキシ基が好ましく、さらに、置換基としてハロゲン原子を有するアルキル基が、線膨張係数が低くなる傾向にあるためより好ましい。また、Ｒ３及びＲ４は同一でも異なっていてもよいが、同一であることが製造容易性の点から好ましい。 (Diamine residue having a partial structure represented by formula (5))
R 3 and R 4 each independently represents an alkyl group, an alkoxy group, an amino group, or a hydroxyl group.
The alkyl group and the alkoxy group each independently preferably have 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low.
Moreover, the alkyl group and the alkoxy group may each have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, it is preferable to have a halogen atom, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Examples of the substituent that the alkoxy group may have include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, a sulfo group, and an allyl group.
Among these, R 3 and R 4 are preferably an alkyl group or an alkoxy group because optical characteristics and a linear expansion coefficient are improved, and an alkyl group having a halogen atom as a substituent tends to have a low linear expansion coefficient. Therefore, it is more preferable. R 3 and R 4 may be the same or different, but are preferably the same from the viewpoint of ease of production.
　式（５）で表される部分構造を有するジアミン残基は特に限定されない。例えば、４，４’－ジアミノ－２，２’－ジメチルビフェニル、４，４’－ジアミノ－２，２’－ジエチルビフェニル、４，４’－ジアミノ－２，２’－ジプロピルビフェニル等のＲ３及びＲ４がアルキル基を有するジアミン化合物；４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、４，４’－ジアミノ－２－メチル－２’－トリフルオロメチルビフェニル等のＲ３及びＲ４がハロゲン化アルキル基を有するジアミン化合物；４，４’－ジアミノ－２，２’－ジメトキシビフェニル、４，４’－ジアミノ－２，２’－ジエトキシビフェニル、アミノ基を有する２，２’，４，４’－テトラアミノビフェニル、水酸基を有する、４，４’－ジアミノ－２，２’－ジヒドロキシビフェニル等のＲ３及びＲ４がアルコキシ基を有するジアミン化合物；等のジアミン化合物から誘導されるジアミン残基が挙げられる。 The diamine residue having a partial structure represented by the formula (5) is not particularly limited. For example, R such as 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-diamino-2,2′-diethylbiphenyl, 4,4′-diamino-2,2′-dipropylbiphenyl, etc. Diamine compounds in which 3 and R 4 have an alkyl group; 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-diamino-2-methyl-2′-trifluoromethylbiphenyl A diamine compound in which R 3 and R 4 each have a halogenated alkyl group; 4,4′-diamino-2,2′-dimethoxybiphenyl, 4,4′-diamino-2,2′-diethoxybiphenyl, an amino group 2,2 ', 4,4'-tetra-aminobiphenyl, a hydroxyl group, the diamine of having R 3 and R 4 are alkoxy groups such as 4,4'-diamino-2,2'-dihydroxybiphenyl with Things; the diamine residue derived from a diamine compound such like.
（式（１）、式（２）、式（３）及び式（４）で表される部分構造以外を有するテトラカルボン酸残基、並びに式（１’）、式（２）、式（４’）及び式（５）で表される部分構造以外を有するテトラカルボン酸残基）
　本発明の主旨を逸脱しない範囲で、式（１）、式（２）、式（３）及び式（４）で表される部分構造以外を有するテトラカルボン酸残基として、下記に示す芳香族テトラカルボン酸二無水物及び脂肪族テトラカルボン酸二無水物等のテトラカルボン酸二無水物から誘導されるテトラカルボン酸残基を用いることができる。
　また、本発明に係る組成物が、式（１’）、式（２）、式（４’）及び式（５）で表される部分構造を有し、テトラカルボン酸残基及びジアミン残基の少なくとも一方は後述する屈曲部位を有する場合、式（１’）、式（２）、式（４’）及び式（５）で表される部分構造以外を有するテトラカルボン酸残基としては、下記に示す芳香族テトラカルボン酸二無水物及び脂肪族テトラカルボン酸二無水物等のテトラカルボン酸二無水物から誘導されるテトラカルボン酸残基及び式（３）で表される部分構造以外を有するテトラカルボン酸残基が挙げられる。 (A tetracarboxylic acid residue having other than the partial structure represented by Formula (1), Formula (2), Formula (3), and Formula (4), and Formula (1 ′), Formula (2), Formula (4 ') And a tetracarboxylic acid residue having other than the partial structure represented by formula (5))
As the tetracarboxylic acid residue having other than the partial structure represented by the formula (1), the formula (2), the formula (3) and the formula (4) without departing from the gist of the present invention, the aromatics shown below Tetracarboxylic acid residues derived from tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides can be used.
Moreover, the composition according to the present invention has a partial structure represented by the formula (1 ′), the formula (2), the formula (4 ′) and the formula (5), a tetracarboxylic acid residue and a diamine residue. In the case where at least one of the following has a bent site, a tetracarboxylic acid residue having other than the partial structure represented by formula (1 ′), formula (2), formula (4 ′) and formula (5), Other than the tetracarboxylic acid residues derived from tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides shown below and partial structures represented by formula (3) The tetracarboxylic acid residue which has is mentioned.
（芳香族テトラカルボン酸二無水物）
　芳香族テトラカルボン酸二無水物としては、例えば、１，２，３，４－ベンゼンテトラカルボン酸二無水物等の分子内に含まれる芳香環が１つであるテトラカルボン酸二無水物；２，２’，６，６’－ビフェニルテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物、２，２’－ビス（トリフルオロメチル）－４，４’，５，５’－ビフェニルテトラカルボン酸二無水物、４，４’－（ヘキサフルオロトリメチレン）－ジフタル酸二無水物、４，４’－（オクタフルオロテトラメチレン）－ジフタル酸二無水物等の独立した２つ以上の芳香環を有するテトラカルボン酸二無水物；１，２，５，６－ナフタレンジカルボン酸二無水物、１，４，５，８－ナフタレンジカルボン酸二無水物、２，３，６，７－ナフタレンジカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、２，３，６，７－アントラセンテトラカルボン酸二無水物、１，２，７，８－フェナントレンテトラカルボン酸二無水物等の縮合芳香環を有するテトラカルボン酸二無水物；等が挙げられる。 (Aromatic tetracarboxylic dianhydride)
Examples of the aromatic tetracarboxylic dianhydride include tetracarboxylic dianhydrides having one aromatic ring in the molecule such as 1,2,3,4-benzenetetracarboxylic dianhydride; , 2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylene) -diphthalic dianhydride, 4,4 '-(octafluorotetramethylene) -diphthalic dianhydride Te having two or more independent aromatic rings such as 1,3,5,6-naphthalenedicarboxylic acid dianhydride, 1,4,5,8-naphthalenedicarboxylic acid dianhydride, 2,3,6,7-naphthalenedicarboxylic acid dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. And tetracarboxylic dianhydride having a condensed aromatic ring.
（脂肪族テトラカルボン酸二無水物）
　脂肪族テトラカルボン酸二無水物としては、例えば、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物等の脂環式テトラカルボン酸二無水物；エチレンテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、ｍｅｓｏ－ブタン－１，２，３，４－テトラカルボン酸二無水物等の鎖状脂肪族テトラカルボン酸二無水物；等が挙げられる。 (Aliphatic tetracarboxylic dianhydride)
Examples of the aliphatic tetracarboxylic dianhydride include alicyclic tetracarboxylic acids such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Dianhydrides; chain aliphatic tetracarboxylic dianhydrides such as ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride And the like.
（式（５）で表される部分構造以外を有するジアミン残基）
　本発明の主旨を逸脱しない範囲で、式（５）で表される部分構造以外を有するジアミン残基として、下記に示すジアミン化合物から誘導されるジアミン残基を用いることができる。 (Diamine residue having other than the partial structure represented by formula (5))
A diamine residue derived from a diamine compound shown below can be used as a diamine residue having a structure other than the partial structure represented by the formula (5) without departing from the gist of the present invention.
　その他のジアミン化合物としては、例えば、１，４－フェニレンジアミン、１，２－フェニレンジアミン、１，３－フェニレンジアミン等の分子内に含まれる芳香環が１つであるジアミン化合物；４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、２，２－ビス（４－（４－アミノフェノキシ）フェニル）プロパン、ビス（４－（４－アミノフェノキシ）フェニル）スルホン、ビス（４－（３－アミノフェノキシ）フェニル）スルホン、１，３－ビス（４－アミノフェノキシ）ネオペンタン、ビス（４－アミノ－３－カルボキシフェニル）メタン、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルフィド、Ｎ－（４－アミノフェノキシ）－４－アミノベンズアミン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、ビス（３－アミノフェニル）スルホン、ノルボルナンジアミン、４，４’－ジアミノ－２－（トリフルオロメチル）ジフェニルエーテル、５－トリフルオロメチル－１，３－ベンゼンジアミン、２，２－ビス（４－（４－アミノフェノキシ）フェニル）ヘキサフルオロプロパン、４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、２，２－ビス［４－｛４－アミノ－２－（トリフルオロメチル）フェノキシ｝フェニル］ヘキサフルオロプロパン、２－トリフルオロメチル－ｐ－フェニレンジアミン、２，２－ビス（３－アミノ－４－メチルフェニル）ヘキサフルオロプロパン、ビス（４－アミノフェニル）アセチレン等の独立した２つ以上の芳香環を有するジアミン化合物；４，４’－（９－フルオレニリデン）ジアニリン、２，７－ジアミノフルオレン、１，５－ジアミノナフタレン、３，７－ジアミノ－２，８－ジメチルジベンゾチオフェン５，５－ジオキシド等の縮合芳香環を有するジアミン化合物；等が挙げられる。 Examples of other diamine compounds include diamine compounds having one aromatic ring contained in the molecule such as 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine; -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, bis (4 -Amino-3-carboxyphenyl) methane, 4,4'-diaminodiphenylsulfone, 4,4'-di Minodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, bis (3-aminophenyl) sulfone, norbornanediamine 4,4′-diamino-2- (trifluoromethyl) diphenyl ether, 5-trifluoromethyl-1,3-benzenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 2- Trifluoromethyl-p-phenylenediamine, 2,2-bis (3-amino-4-methylphenyl) Diamine compounds having two or more independent aromatic rings such as xafluoropropane and bis (4-aminophenyl) acetylene; 4,4 ′-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 1,5- And diamine compounds having a condensed aromatic ring such as diaminonaphthalene and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide.
　式（５）で表される部分構造以外を有するジアミン残基の中でも、光学特性が向上するため、式（６）で表される部分構造を有するジアミン残基を有することが好ましい。 Among diamine residues having other than the partial structure represented by formula (5), it is preferable to have a diamine residue having a partial structure represented by formula (6) in order to improve optical properties.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
［式（６）において、
Ｚは直接結合、スルホニル基、アルキレン基、カルボニル基又はエーテル結合を示し、Ａ及びＢはそれぞれ独立に、直接結合、２価の芳香環、２価の複素環又はフェニルエーテル基を示す。］ [In Formula (6),
Z represents a direct bond, a sulfonyl group, an alkylene group, a carbonyl group or an ether bond, and A and B each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group. ]
　Ｚの中でも、より光学特性を向上させるため、スルホニル基、エーテル結合又はカルボニル基が好ましく、スルホニル基がより好ましい。
　Ｚのアルキレン基としては、特に限定されないが、炭素数１以上であることが好ましく、２以上がさらに好ましい。一方、８以下が好ましく、５以下が更に好ましい。 Among Z, a sulfonyl group, an ether bond or a carbonyl group is preferable, and a sulfonyl group is more preferable in order to further improve optical properties.
The alkylene group for Z is not particularly limited, but preferably has 1 or more carbon atoms, more preferably 2 or more. On the other hand, it is preferably 8 or less, and more preferably 5 or less.
　Ａ及びＢは、それぞれ独立に、直接結合、２価の芳香環、２価の複素環又はフェニルエーテル基を示す。２価の芳香環及び２価の複素環は、置換基を有していてもよい。
　この中でも溶媒への溶解性が高くなる傾向にあるため、フェニルエーテル基が好ましい。Ａ及びＢは、同一でも異なっていてもよいが、同一であることが、製造容易性の点から好ましい。 A and B each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group. The divalent aromatic ring and the divalent heterocyclic ring may have a substituent.
Of these, phenyl ether groups are preferred because they tend to be highly soluble in solvents. A and B may be the same or different, but the same is preferable from the viewpoint of ease of production.
　Ａ及びＢの２価の芳香環としては、具体的にはベンゼン環、ナフタレン環、アントラセン環等が挙げられる。この中でも、溶媒への溶解性が高くなる傾向にあるため、ベンゼン環が好ましい。Ａ及びＢの２価の複素環としては、具体的には、フラン、チオフェン、ピロール、イミダゾール、ピリジン、ピリミジン、ピラジン、オキサゾール、ベンズイミダゾール、ベンズオキサゾール等が挙げられる。 Specific examples of the divalent aromatic rings A and B include a benzene ring, a naphthalene ring, and an anthracene ring. Among these, a benzene ring is preferable because the solubility in a solvent tends to be high. Specific examples of the divalent heterocycle of A and B include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, and benzoxazole.
　式（６）で表される部分構造を有するジアミン残基として、例えば、４，４’－ビス（４－アミノフェノキシ）ビフェニル、４，４’－ビス（３－アミノフェノキシ）ビフェニル、３，３’－ビス（４－アミノフェノキシ）ビフェニル、３，４’－ビス（４－アミノフェノキシ）ビフェニル等のＺが直接結合であるジアミン化合物；３，３’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルホン、３，４’－ジアミノジフェニルスルホン、２，３’－ジアミノジフェニルスルホン、２，４’－ジアミノジフェニルスルホン、ビス（４－（４－アミノフェノキシ）フェニル）スルホン、ビス（４－（３－アミノフェノキシ）フェニル）スルホン等のＺがスルホニル基であるジアミン化合物；２，２－ビス（４－（４－アミノフェノキシ）フェニル）プロパン、２，２－ビス（４－（３－アミノフェノキシ）フェニル）プロパン、１，３－ビス（４－アミノフェノキシ）ネオペンタン、ビス（４－アミノ－３－カルボキシフェニル）メタン等のＺがアルキレン基であるジアミン化合物；４，４’－ジアミノジフェニルケトン、３，４’－ジアミノジフェニルケトン、２，３’－ジアミノジフェニルケトン、２，４’－ジアミノジフェニルケトン等のＺがカルボニル基であるジアミン化合物；３，３’，４，４’－テトラアミノジフェニルケトン、４，４’－ビス（４－アミノフェノキシ）ベンゾフェノン、４，４’－ビス（３－アミノフェノキシ）ベンゾフェノン等のＺがエーテル結合であるジアミン化合物；等のジアミン化合物から誘導されるジアミン残基が挙げられる。 Examples of the diamine residue having a partial structure represented by the formula (6) include 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 3,3 Diamine compounds in which Z is a direct bond such as' -bis (4-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl; 3,3'-diaminodiphenylsulfone, 4,4'-diamino Diphenylsulfone, 3,4'-diaminodiphenylsulfone, 2,3'-diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3 A diamine compound wherein Z is a sulfonyl group, such as -aminophenoxy) phenyl) sulfone; 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 1,3-bis (4-aminophenoxy) neopentan, bis (4-amino-3-carboxyphenyl) methane, etc. A diamine compound wherein Z is an alkylene group; Z such as 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,3′-diaminodiphenyl ketone, 2,4′-diaminodiphenyl ketone, etc. Diamine compounds as groups; 3,3 ′, 4,4′-tetraaminodiphenyl ketone, 4,4′-bis (4-aminophenoxy) benzophenone, 4,4′-bis (3-aminophenoxy) benzophenone, etc. A diamine residue derived from a diamine compound such as a diamine compound in which Z is an ether bond; It is.
（屈曲部位を有する、テトラカルボン酸残基及び／又はジアミン残基）
　本発明の組成物中のポリイミド前駆体及び／又はポリイミドにおいて、屈曲部位を有する、テトラカルボン酸残基及び／又はジアミン残基を有することが、光学特性を向上させる傾向にあるため好ましい。
　本発明において、屈曲部位とは、変形が抑制された屈曲部位であり、屈曲部位を中心とした環の結合角度、屈曲部位に結合した環の面角度、回転、振動等のテトラカルボン酸残基及び／又はジアミン残基を含む分子の動きを抑制するものを言う。中でも、屈曲部位を中心とした環の結合角度及び回転の動きを抑制するものが好ましい。 (Tetracarboxylic acid residue and / or diamine residue having a bent part)
In the polyimide precursor and / or polyimide in the composition of the present invention, it is preferable to have a tetracarboxylic acid residue and / or a diamine residue having a bent portion because the optical properties tend to be improved.
In the present invention, the bending portion is a bending portion in which deformation is suppressed, and a ring bond angle around the bending portion, a ring surface angle bonded to the bending portion, a tetracarboxylic acid residue such as rotation, vibration, etc. And / or those that suppress the movement of molecules containing diamine residues. Among them, those that suppress the ring coupling angle and rotational movement around the bent portion are preferable.
　すなわち、屈曲部位とは環状構造と環状構造に直接結合し、環状構造同士の結合角が１８０度未満となる３価以上の基であることが好ましく、好ましくは１６０度以下、より好ましくは１３０度以下である。特に下限はないが、通常９０度以上である。
　上記角度は、従来既知の計算方法で求めることができる。例えば、ヒュッケル法、拡張ヒュッケル法等の経験的分子軌道法、ハートリーフォック法、配置換相互作用法、多配置ＳＣＦ法等の非経験的分子軌道法、ＰＰＰ近似、ＣＮＤＯ／２、ＩＮＤＯ、ＭＮＤＯ、ＡＭ１、ＰＭ３等の半経験的分子軌道法、ＭＭ２等の分子動力学法、ＢＬＹＰ、Ｂ３ＬＹＰなどの密度汎関数法等が挙げられる。 That is, the bent portion is preferably a trivalent or higher group that is directly bonded to the ring structure and the ring structure, and the bond angle between the ring structures is less than 180 degrees, preferably 160 degrees or less, more preferably 130 degrees. It is as follows. There is no particular lower limit, but it is usually 90 degrees or more.
The angle can be obtained by a conventionally known calculation method. For example, empirical molecular orbital methods such as Hückel method and extended Huckel method, Hartley Fock method, configuration substitution interaction method, ab initio molecular orbital methods such as multi-configuration SCF method, PPP approximation, CNDO / 2, INDO, MNDO And semi-empirical molecular orbital methods such as AM1 and PM3, molecular dynamics methods such as MM2, and density functional methods such as BLYP and B3LYP.
　本発明において、屈曲部位を有することで、ポリイミド前駆体及び／またはポリイミド鎖全体の熱振動が抑制され、線膨張係数が向上する傾向にある。さらに、ポリイミド前駆体及び／またはポリイミド鎖間の相互作用が抑制されることで、透過率、ＹＩ等の光学特性が向上する傾向にあり、同鎖の規則的な配向が乱されることで、リタデーションが向上する傾向にある。
　また、ポリイミド前駆体及び／またはポリイミドの分子鎖の絡まりが増加し、同鎖内の芳香環量が増えることで、耐熱性が向上する傾向にある。 In the present invention, by having a bent portion, thermal vibration of the polyimide precursor and / or the entire polyimide chain is suppressed, and the linear expansion coefficient tends to be improved. Furthermore, by suppressing the interaction between the polyimide precursor and / or the polyimide chain, the optical properties such as transmittance and YI tend to be improved, and the regular orientation of the same chain is disturbed, Retardation tends to improve.
Further, entanglement of molecular chains of the polyimide precursor and / or polyimide increases, and the amount of aromatic rings in the chain increases, so that the heat resistance tends to be improved.
　本発明の組成物中のポリイミド前駆体及び／又はポリイミドは、通常、屈曲部位を有する、テトラカルボン酸残基及びジアミン残基の両方を有していてもよく、屈曲部位を有する、テトラカルボン酸残基又はジアミン残基を有していてもよい。これらの中でも光学特性が向上しやすい傾向にあるため、ジアミン残基が、屈曲部位を有することが好ましい。又、テトラカルボン酸残基及びジアミン残基が、屈曲部位を有することも、光学特性が向上しやすい傾向にあるため好ましい。 The polyimide precursor and / or polyimide in the composition of the present invention may have both a tetracarboxylic acid residue and a diamine residue, which usually have a bending site, and a tetracarboxylic acid having a bending site. It may have a residue or a diamine residue. Among these, since the optical properties tend to be improved, the diamine residue preferably has a bent portion. In addition, it is preferable that the tetracarboxylic acid residue and the diamine residue have a bent portion because the optical characteristics tend to be improved.
　本発明において、テトラカルボン酸残基及び／又はジアミン残基屈曲部位中に屈曲部位を複数有していてもよいが、複数の屈曲部位が、連結していないことが好ましい。屈曲部位が連結しないことで、重合性を維持及び向上することができる傾向にある。
　本発明において、屈曲部位には環状構造が直接結合していることが好ましい。環状構造が直接結合することで、結合角度、屈曲部位に結合した環の面角度、回転、振動等の変形がより抑制される。屈曲部位に直接結合する環状構造は、屈曲部位と同じテトラカルボン酸残基／ジアミン残基由来でもよく、異なっていてもよい。屈曲部位と同じテトラカルボン酸残基／ジアミン残基由来の場合、環状構造はテトラカルボン酸モノマー／ジアミンモノマーが有する構造となる。屈曲部位と同じテトラカルボン酸残基／ジアミン残基由来ではない場合、環状構造は環状イミド構造である。 In the present invention, a tetracarboxylic acid residue and / or diamine residue bending portion may have a plurality of bending portions, but the plurality of bending portions are preferably not connected. It exists in the tendency which can maintain and improve polymerizability by a bending part not connecting.
In the present invention, it is preferable that a cyclic structure is directly bonded to the bent portion. By directly bonding the annular structure, deformations such as a bonding angle, a surface angle of a ring bonded to a bent portion, rotation, vibration, and the like are further suppressed. The cyclic structure directly bonded to the bending site may be derived from the same tetracarboxylic acid residue / diamine residue as the bending site or may be different. When derived from the same tetracarboxylic acid residue / diamine residue as that of the bent part, the cyclic structure is a structure possessed by the tetracarboxylic acid monomer / diamine monomer. When not derived from the same tetracarboxylic acid residue / diamine residue as the bending site, the cyclic structure is a cyclic imide structure.
　屈曲部位を有するテトラカルボン酸残基は、上記式（１）、式（２）、式（３）及び式（４）で表される部分構造を有するテトラカルボン酸残基であってもよく、式（１）、式（２）、式（３）及び式（４）で表される部分構造以外を有するテトラカルボン酸残基であってもよい。
　低線膨張係数及び低リタデーションの両立の点から、好ましくは、屈曲部位を有するテトラカルボン酸残基は、式（１）、式（２）、式（３）及び式（４）で表される部分構造以外を有するテトラカルボン酸残基である。さらに、低線膨張係数及び低リタデーションの両立の点から、屈曲部位を有するテトラカルボン酸残基は、上記式（１’）、式（２）及び式（４’）で表される部分構造以外を有するテトラカルボン酸残基である。
　また、屈曲部位を有するテトラカルボン酸残基を複数有していてもよい。
　屈曲部位を有するジアミン残基は、上記式（５）で表される部分構造以外であり、複数有していてもよい。 The tetracarboxylic acid residue having a bent portion may be a tetracarboxylic acid residue having a partial structure represented by the above formula (1), formula (2), formula (3) and formula (4), It may be a tetracarboxylic acid residue having other than the partial structure represented by formula (1), formula (2), formula (3) and formula (4).
From the viewpoint of achieving both a low linear expansion coefficient and a low retardation, the tetracarboxylic acid residue having a bent portion is preferably represented by the formula (1), the formula (2), the formula (3), and the formula (4). It is a tetracarboxylic acid residue having other than a partial structure. Furthermore, from the viewpoint of achieving both a low linear expansion coefficient and a low retardation, the tetracarboxylic acid residue having a bent portion is other than the partial structure represented by the above formula (1 ′), formula (2) and formula (4 ′). It is a tetracarboxylic acid residue having
Moreover, you may have two or more tetracarboxylic acid residues which have a bending part.
The diamine residue having a bent portion is other than the partial structure represented by the above formula (5), and may have a plurality.
　屈曲部位の含有量は特に制限はないが、組成物中のテトラカルボン酸残基及びジアミン残基の和に対する割合で、通常０．１ｍｏｌ％以上、好ましくは０．５ｍｏｌ％、より好ましくは１ｍｏｌ％以上、さらに好ましくは５ｍｏｌ％以上である。また、通常１５０ｍｏｌ％以下、好ましくは１００ｍｏｌ％以下、より好ましくは５０ｍｏｌ％以下である。これらの範囲であることで、光学特性が良好となり、機械物性が向上する傾向にある。 The content of the bent portion is not particularly limited, but is usually 0.1 mol% or more, preferably 0.5 mol%, more preferably 1 mol%, based on the ratio of the tetracarboxylic acid residue and the diamine residue in the composition. As mentioned above, More preferably, it is 5 mol% or more. Moreover, it is 150 mol% or less normally, Preferably it is 100 mol% or less, More preferably, it is 50 mol% or less. By being in these ranges, the optical properties are improved and the mechanical properties tend to be improved.
　屈曲部位としては、環と結合した、主鎖を構成する元素に３価以上の結合を有することが好ましい。３価以上の結合の中でも、４級炭素原子、６価の硫黄原子、３級アミン、ベンゼン環から選ばれる少なくとも１つが好ましい。特に、屈曲部位を有する、テトラカルボン酸及び／又はジアミン残基が、４級炭素原子及び／又は６価の硫黄原子によって２つ以上の芳香環が結合されるものであることが光学特性を向上させる傾向にあるため好ましい。 As the bending part, it is preferable that the element constituting the main chain bonded to the ring has a trivalent or higher bond. Among the trivalent or higher bonds, at least one selected from a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine, and a benzene ring is preferable. In particular, the optical properties are improved when the tetracarboxylic acid and / or diamine residue having a bent portion is one in which two or more aromatic rings are bonded by a quaternary carbon atom and / or a hexavalent sulfur atom. This is preferable.
　３価以上の結合を有するものは本発明の主旨を逸脱しない限り特に制限はないが、例えば、以下式（３０）で表される構造が挙げられる。 Those having a bond of 3 or more are not particularly limited as long as they do not depart from the gist of the present invention, and examples thereof include a structure represented by the following formula (30).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記式（３０）中、Ｚ１は４級炭素原子、６価の硫黄原子、３級アミン又はベンゼン環を表す。Ｙ１及びＹ２はそれぞれ独立して、環状構造を表す。
　４級炭素としてはヘキサフルオロプロパン、プロパン、フルオレン等が光学特性が向上するため好ましい。６価の硫黄としてはスルホニル基が光学特性が向上するため好ましい。３級アミンとしてはトリメチルアミンが好ましい。 In the above formula (30), Z 1 represents a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine or a benzene ring. Y 1 and Y 2 each independently represent a cyclic structure.
As the quaternary carbon, hexafluoropropane, propane, fluorene and the like are preferable because optical characteristics are improved. As hexavalent sulfur, a sulfonyl group is preferable because optical characteristics are improved. Trimethylamine is preferred as the tertiary amine.
　Ｙ１及びＹ２の環状構造とは、芳香族化合物、脂環系化合物又はイミド環を示す。
　芳香族化合物とは、１つの環を形成する元素数が５以上、８以下であり、単環又は２つの環が縮合していてもよい。具体的には、ベンゼン環、縮合芳香環又は複素環である。
　縮合芳香環の環数は特に限定されないが、２以上、５以下が耐熱性と光学特性が両立できる傾向にあるため好ましい。
　複素環は、特に限定はないが、具体的には、フラン、チオフェン、ピロール、イミダゾール、ピリジン、ピリミジン、ピラジン、オキサゾール、ベンズイミダゾール、ベンズオキサゾール等が挙げられる。
　芳香族化合物が有していてもよい置換基は、炭素数１以上、６以下のアルキル基、炭素数１以上、６以下のアルコキシ基、アミノ基、ヒドロキシル基等が挙げられる。
　炭素数１以上、６以下のアルキル基及び炭素数１以上、６以下のアルコキシ基は置換基を有していてもよい。
　炭素数１以上、６以下のアルキル基が有していてもよい置換基は、ハロゲン原子、水酸基等が挙げられる。
　炭素数１以上、６以下のアルコキシ基が有していてもよい置換基は、ハロゲン原子、水酸基等が挙げられる。 The cyclic structure of Y 1 and Y 2 represents an aromatic compound, an alicyclic compound, or an imide ring.
With the aromatic compound, the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a condensed aromatic ring or a heterocyclic ring.
The number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
The heterocyclic ring is not particularly limited, and specific examples include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
Examples of the substituent that the aromatic compound may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a hydroxyl group.
The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may have a substituent.
Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
Examples of the substituent that the alkoxy group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
　脂環系化合物とは、１つの環を形成する炭素数が４以上、８以下であり、単環又は２つの環が縮合していてもよい。また、環中に不飽和結合を有していてもよい。
　具体的には、シクロブタン、シクロブタジエン、シクロペンタン、シクロペンタエン、シクロヘキサン、シクロヘキサエン、シクロヘキサジエン、シクロヘプタン、シクロヘプタエン、シクロオクタン等が挙げられる。
　脂環系化合物は、置換基を有していてもよく、有していてもよい置換基としては、炭素数１以上、６以下のアルキル基、炭素数１以上、６以下のアルコキシ基、アミノ基、ヒドロキシル基等が挙げられる。炭素数１以上、６以下のアルキル基及び炭素数１以上、６以下のアルコキシ基は置換基を有していてもよく、有していてもよい置換基としては、上記芳香族化合物で挙げたものと同義である。 The alicyclic compound has 4 or more and 8 or less carbon atoms forming one ring, and a single ring or two rings may be condensed. Moreover, you may have an unsaturated bond in the ring.
Specific examples include cyclobutane, cyclobutadiene, cyclopentane, cyclopentaene, cyclohexane, cyclohexaene, cyclohexadiene, cycloheptane, cycloheptaene, cyclooctane, and the like.
The alicyclic compound may have a substituent, and examples of the substituent that may be included include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino group. Group, hydroxyl group and the like. The alkyl group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 6 or less carbon atoms may have a substituent, and examples of the substituent that may have may include the above-mentioned aromatic compounds. Synonymous with things.
　イミド環とは、イミド結合を有する環であり、１つの環を形成する元素数が４以上、６以下であり、イミド環のみでもよく、他の環と縮合していてもよい。縮合していてもよい環としては、置換基を有していてもよい芳香族化合物、置換基を有していてもよい脂環系化合物である。縮合する場合の環数は特に限定されないが、２以上、４以下が、耐熱性と光学特性が両立できる傾向にあるため好ましい。 An imide ring is a ring having an imide bond, and the number of elements forming one ring is 4 or more and 6 or less, and may be only an imide ring or may be condensed with another ring. The ring which may be condensed includes an aromatic compound which may have a substituent and an alicyclic compound which may have a substituent. The number of rings in the case of condensation is not particularly limited, but is preferably 2 or more and 4 or less because heat resistance and optical properties tend to be compatible.
　式(３０)で表される構造の中でも、下記式（３１）～（３５）で表される構造から選ばれる部位であることが光学特性向上の点から好ましい。 Among the structures represented by the formula (30), a site selected from the structures represented by the following formulas (31) to (35) is preferable from the viewpoint of improving optical properties.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（３１）中、Ｒ１０、Ｒ１１はそれぞれ独立に、アルキル基、アミノ基又はヒドロキシル基を表し、Ｙ１及びＹ２はそれぞれ独立して、芳香族炭化水素、脂環系化合物又はイミド環を表す。
　Ｒ１０、Ｒ１１のアルキル基は、炭素数１以上が好ましい。一方、１０以下が好ましく、８以下が更に好ましく、６以下が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にあるため好ましい。また、アルキル基は、置換基を有していてもよい。アルキル基が有していてもよい置換基としては、ハロゲン原子、シアノ基、ニトロ基、スルホ基等が挙げられる。これらの中でも無置換又はハロゲン原子を有することが好ましく、フッ素原子が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にある。
　Ｙ１及びＹ２は、式（３０）のＹ１及びＹ２とそれぞれ同義であり、具体例、好ましい範囲及び有していてもよい置換基も同義である。 In formula (31), R 10 and R 11 each independently represents an alkyl group, an amino group or a hydroxyl group, and Y 1 and Y 2 each independently represent an aromatic hydrocarbon, an alicyclic compound or an imide ring. Represents.
The alkyl group for R 10 and R 11 preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low. Moreover, the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, unsubstituted or preferably having a halogen atom is preferable, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（３２）中、Ｒ１２～Ｒ１５はそれぞれ独立に、アルキル基又はヒドロキシル基を示す。
　Ｒ１２～Ｒ１５のアルキル基は、それぞれ独立に、炭素数１以上が好ましい。一方、１０以下が好ましく、８以下が更に好ましく、６以下が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にあるため好ましい。また、アルキル基は、置換基を有していてもよい。アルキル基が有していてもよい置換基としては、ハロゲン原子、シアノ基、ニトロ基、スルホ基等が挙げられる。これらの中でもハロゲン原子を有することが好ましく、フッ素原子が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にある。
　Ｙ１及びＹ２は、式（３０）のＹ１及びＹ２とそれぞれ同義であり、具体例、好ましい範囲及び有していてもよい置換基も同義である。 In the formula (32), R 12 to R 15 each independently represents an alkyl group or a hydroxyl group.
The alkyl groups for R 12 to R 15 each independently preferably have 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low. Moreover, the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, it is preferable to have a halogen atom, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（３３）中、Ｙ１及びＹ２は、式（３０）のＹ１及びＹ２とそれぞれ同義であり、具体例、好ましい範囲及び有していてもよい置換基も同義である。 Wherein (33), Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（３４）中、Ｒ１６はアルキル基又は芳香族化合物を示す。Ｙ１及びＹ２は、式（３０）のＹ１及びＹ２とそれぞれ同義であり、具体例、好ましい範囲及び有していてもよい置換基も同義である。
　Ｒ１６のアルキル基は、炭素数１以上が好ましい。一方、１０以下が好ましく、８以下が更に好ましく、６以下が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にあるため好ましい。また、アルキル基は、置換基を有していてもよい。アルキル基が有していてもよい置換基としては、ハロゲン原子、シアノ基、ニトロ基、スルホ基等が挙げられる。これらの中でもハロゲン原子を有することが好ましく、フッ素原子が特に好ましい。この範囲であることで、線膨張係数が低くなる傾向にある。
　Ｒ１６の芳香族化合物は、１つの環を形成する元素数が５以上、８以下であり、単環又は２つの環が縮合していてもよい。具体的には、ベンゼン環、縮合芳香環又は複素環である。これらの中でも、単環のベンゼン環、ベンゼン環が縮合した縮合芳香環が線膨張係数が低くなる傾向にあるため好ましい。
　縮合芳香環の環数は特に限定されないが、２以上、５以下が耐熱性と光学特性が両立できる傾向にあるため好ましい。
　複素環は、特に限定はないが、具体的には、フラン、チオフェン、ピロール、イミダゾール、ピリジン、ピリミジン、ピラジン、オキサゾール、ベンズイミダゾール、ベンズオキサゾール等が挙げられる。
　芳香族化合物が有していてもよい置換基は、炭素数１以上、６以下のアルキル基、炭素数１以上、６以下のアルコキシ基、アミノ基、ヒドロキシル基等が挙げられる。
　炭素数１以上、６以下のアルキル基及び炭素数１以上、６以下のアルコキシ基は置換基を有していてもよい。
　炭素数１以上、６以下のアルキル基が有していてもよい置換基は、ハロゲン原子、水酸基等が挙げられる。
　炭素数１以上、６以下のアルコキシ基が有していてもよい置換基は、ハロゲン原子、水酸基等が挙げられる。 In the formula (34), R 16 represents an alkyl group or an aromatic compound. Y 1 and Y 2 are each as Y 1 and Y 2 of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
The alkyl group for R 16 preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is more preferable, and 6 or less is particularly preferable. This range is preferable because the linear expansion coefficient tends to be low. Moreover, the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, a nitro group, and a sulfo group. Among these, it is preferable to have a halogen atom, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
In the aromatic compound of R 16, the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a condensed aromatic ring or a heterocyclic ring. Among these, a monocyclic benzene ring or a condensed aromatic ring obtained by condensing a benzene ring is preferable because the coefficient of linear expansion tends to be low.
The number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
The heterocyclic ring is not particularly limited, and specific examples include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
Examples of the substituent that the aromatic compound may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a hydroxyl group.
The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may have a substituent.
Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
Examples of the substituent that the alkoxy group having 1 to 6 carbon atoms may have include a halogen atom and a hydroxyl group.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（３５）中、Ｒは、アルキル基、ニトロ基、アミノ基、水酸基又はハロゲン原子を示す。 In the formula (35), R represents an alkyl group, a nitro group, an amino group, a hydroxyl group or a halogen atom.
　前記アルキル基としては、特に限定されないが、炭素数１以上であることが好ましい。一方、８以下が好ましく、５以下が更に好ましい。これらの範囲であることで、溶媒との相溶性が良くなる傾向にある。
　アルキル基は置換基を有していてもよく、例えば、アミノ基、ヒドロキシル基、ニトロ基、ハロゲン原子等が挙げられる。 The alkyl group is not particularly limited, but preferably has 1 or more carbon atoms. On the other hand, it is preferably 8 or less, and more preferably 5 or less. By being in these ranges, the compatibility with the solvent tends to be improved.
The alkyl group may have a substituent, and examples thereof include an amino group, a hydroxyl group, a nitro group, and a halogen atom.
　式（３５）で表される構造を有するジアミン残基としては、例えば、２，６－ジアミノトルエン、２，５－ジアミノトルエン、２，４－ジアミノトルエン、３，４－ジアミノトルエン、２，３－ジアミノトルエン、４－フルオロ－１，２－フェニレンジアミン、４－フルオロ－１，３―フェニレンジアミン、４－ニトロ－１，２－フェニレンジアミン、４－ニトロ－１，３－フェニレンジアミン、２－ニトロ－１，２－フェニレンジアミン、３－トリフルオロメチル－１，５－フェニレンジアミン、４－トリフルオロメチル－１，５－フェニレンジアミン、４―トリフルオロメチル－１，２－フェニレンジアミン、３－ヒドロキシ－１，５－フェニレンジアミン、４－ヒドロキシ－１，５－フェニレンジアミン、４―ヒドロキシ－１，２－フェニレンジアミン等のジアミン化合物から誘導されたジアミン残基が挙げられる。 Examples of the diamine residue having the structure represented by the formula (35) include 2,6-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,3 -Diaminotoluene, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 2- Nitro-1,2-phenylenediamine, 3-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 3- Hydroxy-1,5-phenylenediamine, 4-hydroxy-1,5-phenylenediamine, 4-hydroxy-1,2- Derived diamine residue from a diamine compound such Enirenjiamin like.
　２つ以上の芳香環が４級炭素原子によって結合されたテトラカルボン酸残基としては、例えば、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物、４，４’－イソプロピリデンジフタル酸無水物、２，２－ビス（３，４－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物等のテトラカルボン酸二無水物から誘導されたテトラカルボン酸残基が挙げられる。 Examples of the tetracarboxylic acid residue in which two or more aromatic rings are bonded by a quaternary carbon atom include 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 4,4′-isopropylpropylene. Redene diphthalic anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3 A tetracarboxylic acid residue derived from a tetracarboxylic dianhydride such as -dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.
　２つ以上の芳香環が６価の硫黄原子によって結合されたテトラカルボン酸残基としては、例えば、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、２，３，３’，４’－ジフェニルスルホンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルスルホンテトラカルボン酸二無水物、４，４’－［ｐ－スルホニルビス（フェニレンスルファニル）］ジフタル酸無水物、３，３’－［ｐ－スルホニルビス（フェニレンスルファニル）］ジフタル酸無水物等のテトラカルボン酸二無水物から誘導されたテトラカルボン酸残基が挙げられる。 Examples of the tetracarboxylic acid residue in which two or more aromatic rings are bonded by a hexavalent sulfur atom include, for example, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ', 4'-Diphenylsulfonetetracarboxylic dianhydride, 2,2', 3,3'-diphenylsulfonetetracarboxylic dianhydride, 4,4 '-[p-sulfonylbis (phenylenesulfanyl)] diphthalic acid And tetracarboxylic acid residues derived from tetracarboxylic dianhydrides such as anhydrides and 3,3 ′-[p-sulfonylbis (phenylenesulfanyl)] diphthalic anhydride.
　２つ以上の芳香環が４級炭素原子によって結合されたジアミン残基としては、例えば、２、２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（３－アミノフェニル）プロパン、１，３－ビス［２－（４－アミノフェニル）－２－プロピル］ベンゼン、１，４－ビス［２－（４－アミノフェニ）－２－プロピル］ベンゼン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（３―アミノ－４－ヒドロキシフェニル）プロパン、９，９－ビス（４－アミノフェニル）フルオレン、９，９－ビス（３－アミノフェニル）フルオレン、９，９－ビス（２－アミノフェニル）フルオレン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－｛４－アミノ－２－（トリフルオロメチル）フェノキシ｝フェニル］ヘキサフルオロプロパン、２，２－ビス｛４－（４－アミノフェノキシ）－３，５－ジブロモフェニル｝ヘキサフルオロプロパン等のジアミン化合物から誘導されたジアミン残基が挙げられる。 Examples of the diamine residue in which two or more aromatic rings are bonded by a quaternary carbon atom include 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexa Fluoropropane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminopheny) -2-propyl] benzene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) propane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (2-aminophenyl) Nyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- From diamine compounds such as {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane and 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} hexafluoropropane Derived diamine residues are mentioned.
　２つ以上の芳香環が６価の硫黄原子によって繋がれたジアミン残基としては、例えば、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、３，４’－ジアミノジフェニルスルホン、４，４’－ビス（４－アミノフェニレンスルファニル）ジフェニルスルホン、３，３’－ビス（４－アミノフェニレンスルファニル）ジフェニルスルホン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、３，３’，４，４’－テトラアミノジフェニルスルホン等のジアミン化合物から誘導されたジアミン残基が挙げられる。 Examples of the diamine residue in which two or more aromatic rings are connected by a hexavalent sulfur atom include, for example, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, and 3,4′-diaminodiphenylsulfone. 4,4′-bis (4-aminophenylenesulfanyl) diphenylsulfone, 3,3′-bis (4-aminophenylenesulfanyl) diphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4 Derived from diamine compounds such as-(3-aminophenoxy) phenyl] sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 3,3 ', 4,4'-tetraaminodiphenylsulfone A diamine residue is mentioned.
（組成物に含まれるポリイミド前駆体及び／又はポリイミドの物性）
　組成物に含まれるポリイミド前駆体及び／又はポリイミドの重量平均分子量（Ｍｗ）は特に制限されないが、ポリスチレン換算の重量平均分子量で通常１０００以上、好ましくは３０００以上、より好ましくは５０００以上、さらに好ましくは１００００以上である。また、通常２０００００以下であり、好ましくは１８００００以下であり、より好ましくは１５００００以下である。この範囲となることで、溶解性、溶液粘度、組成物粘度、溶融粘度等が通常の製造設備で扱いやすい範囲となるため好ましい。なおポリスチレン換算の重量平均分子量は、ゲル浸透クロマトグラフィ（ＧＰＣ）により求めることができる。 (Physical properties of polyimide precursor and / or polyimide contained in the composition)
The weight average molecular weight (Mw) of the polyimide precursor and / or polyimide contained in the composition is not particularly limited, but is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, more preferably, in terms of polystyrene equivalent weight average molecular weight. 10,000 or more. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150,000 or less. By being in this range, the solubility, solution viscosity, composition viscosity, melt viscosity, and the like are in a range that can be easily handled by ordinary production equipment, which is preferable. The polystyrene-reduced weight average molecular weight can be determined by gel permeation chromatography (GPC).
　組成物に含まれるポリイミド前駆体及び／又はポリイミドの数平均分子量（Ｍｎ）は特に限定されないが、ポリスチレン換算の数平均分子量で通常５００以上、好ましくは１０００以上、より好ましくは２５００以上、さらに好ましくは５０００以上である。また、通常１０００００以下、好ましくは９００００以下、より好ましくは８００００以下である。この範囲となることで、溶解性、溶液粘度、組成物粘度、溶融粘度等が通常の製造設備で扱いやすい範囲となるため好ましい。ポリイミド前駆体及び／又はポリイミドの数平均分子量は、前記重量平均分子量と同様の方法で測定することができる。 The number average molecular weight (Mn) of the polyimide precursor and / or polyimide contained in the composition is not particularly limited, but is usually 500 or more, preferably 1000 or more, more preferably 2500 or more, more preferably, in terms of number average molecular weight in terms of polystyrene. It is 5000 or more. Moreover, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in this range, solubility, solution viscosity, composition viscosity, melt viscosity, and the like are in a range that can be easily handled by ordinary production equipment, which is preferable. The number average molecular weight of the polyimide precursor and / or polyimide can be measured by the same method as the weight average molecular weight.
　組成物に含まれるポリイミド前駆体及び／又はポリイミドの分子量分布（ＰＤＩ、（重量平均分子量／数平均分子量（Ｍｗ／Ｍｎ）））は、通常１以上、好ましくは１．１以上、より好ましくは１．２以上であり、通常１０以下、好ましくは９以下、より好ましくは８以下である。均一性の高い組成物が得られる傾向にあるという点で、分子量分布がこの範囲にあることが好ましい。また、膜の白化防止においては、上記範囲にあることで、膜中成分の均一性、白化抑制及び膜の平滑性に優れた膜が得られる傾向にある。なお、ポリイミド前駆体前駆体及び／又はポリイミドの分子量分布は、前記重量平均分子量と数平均分子量の値から求めることができる。 The molecular weight distribution (PDI, (weight average molecular weight / number average molecular weight (Mw / Mn))) of the polyimide precursor and / or polyimide contained in the composition is usually 1 or more, preferably 1.1 or more, more preferably 1 .2 or more, usually 10 or less, preferably 9 or less, more preferably 8 or less. The molecular weight distribution is preferably in this range in that a composition with high uniformity tends to be obtained. Further, in the prevention of whitening of the film, being in the above range tends to obtain a film excellent in uniformity of components in the film, suppression of whitening and smoothness of the film. In addition, the molecular weight distribution of a polyimide precursor precursor and / or a polyimide can be calculated | required from the value of the said weight average molecular weight and a number average molecular weight.
　ポリイミド前駆体組成物に含まれるポリイミド前駆体のイミド化率は、特に制限はない。通常１００％未満、好ましくは８０％以下、より好ましくは６０％以下であり、さらに好ましくは５０％以下であり、下限はなく、イミド化率が０％でもよい。イミド化率がこの範囲となることで、ポリイミド前駆体組成物に用いる溶媒への溶解性が高くなり、ポリイミド前駆体組成物の安定性が増す傾向にあるため好ましい。ポリイミド前駆体組成物に含まれるポリイミド前駆体のイミド化率は、従来既知の方法、例えばＮＭＲ法、ＩＲ法及び滴定法等で求めることができる。 There is no restriction | limiting in particular in the imidation rate of the polyimide precursor contained in a polyimide precursor composition. Usually, it is less than 100%, preferably 80% or less, more preferably 60% or less, and further preferably 50% or less. There is no lower limit, and the imidation rate may be 0%. It is preferable for the imidization ratio to be in this range because solubility in a solvent used for the polyimide precursor composition is increased and the stability of the polyimide precursor composition tends to increase. The imidation ratio of the polyimide precursor contained in the polyimide precursor composition can be determined by a conventionally known method such as the NMR method, the IR method, and the titration method.
（ポリイミド前駆体及び／又はポリイミド組成物のその他の成分）
　本発明のポリイミド前駆体及び／又はポリイミド組成物は、上述したポリイミド前駆体及び／又はポリイミド及び溶媒以外に、本発明の効果を損なわない限りその他の成分を含むことができる。その他の成分としては、例えば、界面活性剤、溶媒、酸化防止剤、滑剤、着色剤、安定剤、紫外線吸収剤、帯電防止剤、難燃剤、可塑剤、離型剤、レベリング剤、消泡剤等が挙げられる。また、その他必要に応じて、発明の目的を損なわない範囲で、粉末状、粒状、板状及び繊維状等の無機系充填剤又は有機系充填剤を配合してもよい。これらの添加成分は、ポリイミド前駆体及び／又はポリイミド組成物を製造するどの工程のどの段階で添加してもよい。 (Polyimide precursor and / or other components of polyimide composition)
The polyimide precursor and / or polyimide composition of the present invention can contain other components in addition to the polyimide precursor and / or polyimide and solvent described above as long as the effects of the present invention are not impaired. Examples of other components include surfactants, solvents, antioxidants, lubricants, colorants, stabilizers, UV absorbers, antistatic agents, flame retardants, plasticizers, mold release agents, leveling agents, and antifoaming agents. Etc. Moreover, you may mix | blend inorganic type fillers or organic type fillers, such as a powder form, a granular form, plate shape, and a fiber form, as long as the objective of invention is not impaired as needed. These additive components may be added at any stage of any process for producing a polyimide precursor and / or a polyimide composition.
　これらの成分の中で、レベリング剤を含むことが膜の平滑性が向上する傾向となるため好ましい。レベリング剤としては、例えばシリコーン系化合物等が挙げられる。シリコーン系化合物は特に限定はないが、例えば、ポリエーテル変性シロキサン、ポリエーテル変性ポリジメチルシロキサン、ポリエーテル変性水酸基含有ポリジメチルシロキサン、ポリエーテル変性ポリメチルアルキルシロキサン、ポリエステル変性ポリジメチルシロキサン、ポリエステル変性水酸基含有ポリジメチルシロキサン、ポリエステル変性ポリメチルアルキルシロキサン、アラルキル変性ポリメチルアルキルシロキサン、高重合シリコーン、アミノ変性シリコーン、アミノ誘導体シリコーン、フェニル変性シリコーン及びポリエーテル変性シリコーン等が挙げられる。 Among these components, it is preferable to include a leveling agent because the smoothness of the film tends to be improved. Examples of the leveling agent include silicone compounds. The silicone compound is not particularly limited. For example, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyether-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified hydroxyl group Examples thereof include polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, highly polymerized silicone, amino-modified silicone, amino-derivative silicone, phenyl-modified silicone, and polyether-modified silicone.
（組成物に含まれるポリイミド前駆体の製造）
　テトラカルボン酸二無水物とジアミン化合物からポリイミド前駆体を得る反応は、従来から知られている条件で行うことができる。テトラカルボン酸二無水物とジアミン化合物の添加順序や添加方法には特に限定はない。例えば、溶媒にテトラカルボン酸二無水物とジアミン化合物を順に投入し、適切な温度で撹拌することにより、ポリイミド前駆体は得られる。 (Production of polyimide precursor contained in the composition)
Reaction which obtains a polyimide precursor from tetracarboxylic dianhydride and a diamine compound can be performed on conventionally known conditions. There are no particular limitations on the order of addition or addition method of the tetracarboxylic dianhydride and the diamine compound. For example, a polyimide precursor can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.
　ジアミン化合物の量は、テトラカルボン酸二無水物１ｍｏｌに対して、通常０．７ｍｏｌ以上、好ましくは０．８ｍｏｌ以上であり、通常１．３ｍｏｌ以下、好ましくは１．２ｍｏｌ以下である。ジアミン化合物をこのような範囲とすることで、得られるポリイミド前駆体の収率が向上する傾向にある。
　ジアミン化合物の量がこの範囲にあることで、組成物の粘度が塗布に適した範囲になりやすく、また強靭なフィルムが得やすい傾向にある。 The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. By making a diamine compound into such a range, it exists in the tendency for the yield of the polyimide precursor obtained to improve.
When the amount of the diamine compound is within this range, the viscosity of the composition tends to be in a range suitable for coating, and a tough film tends to be easily obtained.
　溶媒中のテトラカルボン酸二無水物及びジアミン化合物の濃度は、反応条件やポリイミド前駆体の粘度に応じて適宜設定できる。例えば、テトラカルボン酸二無水物とジアミン化合物の合計の質量％は特に制限されないが、全液量に対し、通常１質量％以上、好ましくは５質量％以上であり、通常７０質量％以下、好ましくは５０質量％以下、より好ましくは４０質量％以下である。反応基質をこの範囲とすることによって、低コストで収率よくポリイミド前駆体を得ることができる。さらには分子量の伸長が起こりやすい傾向にあり、粘度が高くなり過ぎず、溶液の撹拌が容易である傾向にもある。 The concentration of tetracarboxylic dianhydride and diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the polyimide precursor. For example, the total mass% of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably with respect to the total liquid amount. Is 50% by mass or less, more preferably 40% by mass or less. By setting the reaction substrate within this range, a polyimide precursor can be obtained at a low cost and with a high yield. Furthermore, the molecular weight tends to elongate, the viscosity does not become too high, and the solution tends to be easily stirred.
　反応温度は、反応が進行する温度であれば特に制限はないが、通常０℃以上、好ましくは２０℃以上であり、通常１２０℃以下、好ましくは１００℃以下である。反応時間は通常１時間以上、好ましくは２時間以上であり、通常１００時間以下、好ましくは４２時間以下であり、より好ましくは２４時間以下である。このような条件で反応を行うことによって、低コストで収率よくポリイミド前駆体を得ることができる。
　反応時の圧力は、常圧、加圧又は減圧のいずれかでもよい。
　雰囲気は空気下でも不活性雰囲気下でもよい。 The reaction temperature is not particularly limited as long as the reaction proceeds, but is usually 0 ° C or higher, preferably 20 ° C or higher, and usually 120 ° C or lower, preferably 100 ° C or lower. The reaction time is usually 1 hour or more, preferably 2 hours or more, usually 100 hours or less, preferably 42 hours or less, more preferably 24 hours or less. By performing the reaction under such conditions, a polyimide precursor can be obtained at low cost and high yield.
The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure.
The atmosphere may be air or an inert atmosphere.
　この反応で用いる溶媒としては特に限定されないが、例えば、ヘキサン、シクロヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、メシチレン、アニソール等の炭化水素系溶媒；四塩化炭素、塩化メチレン、クロロホルム、１，２－ジクロロエタン、クロロベンゼン、ジクロロベンゼン、フルオロベンゼン等のハロゲン化炭化水素溶媒；ジエチルエーテル、テトラヒドロフラン、１，４－ジオキサン、メトキシベンゼン等のエーテル系溶媒；アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソブチルケトン等のケトン系溶媒；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド系溶媒；ジメチルスルホキシド等の非プロトン系極性溶媒；ピリジン、ピコリン、ルチジン、キノリン、イソキノリン等の複素環系溶媒；フェノール、クレゾール等のフェノール系溶媒；γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン等のラクトン系溶媒等が挙げられる。これらの溶媒は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 The solvent used in this reaction is not particularly limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomer Glycol solvents such as ether acetate; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Aprotic polar solvents such as dimethyl sulfoxide; Pyridine, picoline, lutidine And heterocyclic solvents such as quinoline and isoquinoline; phenol solvents such as phenol and cresol; lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone. These solvents may be used alone or in combination of two or more in any ratio and combination.
　得られたポリイミド前駆体はそのまま用いてもよく、また貧溶媒中に添加することで固体状に析出させた後に他の溶媒に再溶解させてポリイミド前駆体組成物として得ることもできる。
　この時の貧溶媒は特に制限はなく、ポリイミド前駆体の種類によって適宜選択し得るが、ジエチルエーテル又はジイソプロピルエーテル等のエーテル系溶媒；アセトン、メチルエチルケトン、イソブチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、イソプロピルアルコール等のアルコール系溶媒等が挙げられる。中でも、イソプロピルアルコール等のアルコール系溶媒が効率よく析出物がえられ、沸点が低く乾燥が容易である点で好ましい。これらの溶媒は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 The obtained polyimide precursor may be used as it is, or may be added to a poor solvent to be precipitated in a solid state and then re-dissolved in another solvent to obtain a polyimide precursor composition.
The poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of the polyimide precursor, but an ether solvent such as diethyl ether or diisopropyl ether; a ketone solvent such as acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone; Examples thereof include alcohol solvents such as methanol, ethanol, isopropyl alcohol and the like. Among them, alcohol solvents such as isopropyl alcohol are preferable in that precipitates can be obtained efficiently, the boiling point is low, and drying is easy. These solvents may be used alone or in combination of two or more in any ratio and combination.
　ポリイミド前駆体を溶解させる溶媒は特に限定されないが、例えば、ヘキサン、シクロヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、メシチレン、アニソール等の炭化水素系溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド系溶媒；ジメチルスルホキシド等の非プロトン系溶媒；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系溶媒；等が挙げられる。この中でも特にアニソール、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、エチレングリコールジメチルエーテル及びエチレングリコールモノメチルエーテルが好ましい。これらの溶媒は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 The solvent for dissolving the polyimide precursor is not particularly limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as N-methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate Solvent; and the like. Of these, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether and ethylene glycol monomethyl ether are particularly preferable. These solvents may be used alone or in combination of two or more in any ratio and combination.
　本発明の組成物は、本発明の主旨を逸脱しない限りその他の溶媒を含んでもよい。その種類は特に限定されないが、塗工性が良くなるためアルコールが好ましい。
　アルコールとしては特に制限はない。２０℃における蒸気圧は特に制限はないが、好ましくは５００００Ｐａ以下、より好ましくは２００００Ｐａ以下、さらに好ましくは１００００Ｐａ以下、より好ましくは５０００Ｐａ以下である。また、下限はなく、低い方が好ましいが、例えば１Ｐａ以上である。蒸気圧がこの範囲であることで、組成物及びフィルム中成分の均一性、白化抑制、並びに平滑性に優れたフィルムが得られる傾向にある。 The composition of the present invention may contain other solvents without departing from the gist of the present invention. The type is not particularly limited, but alcohol is preferred because of good coatability.
There is no restriction | limiting in particular as alcohol. The vapor pressure at 20 ° C. is not particularly limited, but is preferably 50000 Pa or less, more preferably 20000 Pa or less, further preferably 10,000 Pa or less, and more preferably 5000 Pa or less. Moreover, there is no lower limit, and the lower one is preferable, but it is, for example, 1 Pa or more. When the vapor pressure is within this range, a film excellent in uniformity of the composition and in-film components, whitening suppression, and smoothness tends to be obtained.
　組成物に添加するアルコールの沸点は特に制限はないが、好ましくは６０℃以上、より好ましくは１００℃以上、さらに好ましくは１２０℃以上である。また好ましくは３００℃以下、より好ましくは２８０℃以下、さらに好ましくは２５０℃以下である。
　沸点がこの範囲であることで、塗布等のフィルム形成時のポリイミド前駆体組成物の濃度変化が少なくなり、そのためフィルム中成分の均一性、白化抑制及び膜の平滑性に優れた膜が得られる傾向にある。さらに、乾燥後や加熱後のフィルム中の残留溶媒が少なくなる傾向にある。 The boiling point of the alcohol added to the composition is not particularly limited, but is preferably 60 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. Moreover, Preferably it is 300 degrees C or less, More preferably, it is 280 degrees C or less, More preferably, it is 250 degrees C or less.
When the boiling point is within this range, the concentration change of the polyimide precursor composition during film formation such as coating is reduced, so that a film excellent in uniformity of components in the film, suppression of whitening and smoothness of the film can be obtained. There is a tendency. Furthermore, the residual solvent in the film after drying or heating tends to decrease.
　組成物に添加するアルコールのオクタノール／水分配係数（ｌｏｇρ）は特に制限はないが、好ましくは０以上、より好ましくは０．５以上、さらに好ましくは１以上である。また上限はなく、大きい方が好ましい。ｌｏｇρがこの範囲であることで、フィルムへの水分の影響が少なくなり、フィルム形成時の白化が抑制される傾向にある。 The octanol / water partition coefficient (log ρ) of the alcohol added to the composition is not particularly limited, but is preferably 0 or more, more preferably 0.5 or more, and even more preferably 1 or more. There is no upper limit, and a larger one is preferred. When log ρ is within this range, the influence of moisture on the film is reduced, and whitening during film formation tends to be suppressed.
　組成物に添加するアルコールの全溶媒に対する割合は特に制限はないが、５０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。また、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１．０質量％以上がさらに好ましい。この範囲であることで、ポリイミド前駆体及び／またはポリイミドの溶解性が高くなり、またフィルム形成時の白化が抑制される傾向にある。 The ratio of alcohol added to the composition with respect to the total solvent is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. Moreover, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1.0 mass% or more is further more preferable. By being in this range, the solubility of the polyimide precursor and / or polyimide is increased, and whitening during film formation tends to be suppressed.
　組成物に添加するアルコールは、芳香族アルコール、脂肪族アルコール及びグリコールモノエーテル系アルコールからなる群より選ばれる１種以上であることが好ましい。これらの溶媒は、単独で用いてもよく、任意の割合で併用してもよい。
　中でも、ポリイミド前駆体及び／又はポリイミドの溶解性が高くなるため、脂肪族アルコール又はグリコールモノエーテル系アルコールが好ましく、特に脂肪族アルコールが好ましい。
　脂肪族アルコールの中でも、炭素数が４以上であることが好ましく、炭素数が５以上であることがより好ましい。また２０以下であることが好ましく、１５以下であることが更に好ましい。
　また、脂肪族アルコールの中でも、環状及び分岐を有することが好ましく、分岐の場合、分岐位置がβ及び／またはγ位であることが特に好ましい。
　上記のように適当な炭素数及び／又は置換位置を有することで、ポリイミド前駆体及び／又はポリイミドの溶解性が高くなる傾向にある。 The alcohol added to the composition is preferably at least one selected from the group consisting of aromatic alcohols, aliphatic alcohols and glycol monoether alcohols. These solvents may be used alone or in combination at any ratio.
Especially, since the solubility of a polyimide precursor and / or a polyimide becomes high, an aliphatic alcohol or glycol monoether type alcohol is preferable, and an aliphatic alcohol is especially preferable.
Among aliphatic alcohols, the number of carbon atoms is preferably 4 or more, and more preferably 5 or more. Moreover, it is preferable that it is 20 or less, and it is still more preferable that it is 15 or less.
Moreover, among aliphatic alcohols, it is preferable to have a ring and a branch, and in the case of a branch, it is particularly preferable that the branch position is β and / or γ.
By having an appropriate carbon number and / or substitution position as described above, the solubility of the polyimide precursor and / or polyimide tends to increase.
　組成物に添加するアルコールは特に限定されないが、具体的には以下が挙げられる。
（芳香族アルコール）
　芳香族アルコールとしては、ベンジルアルコール、サリチルアルコール、ジフェニルメタノール、及びバニリルアルコール等が挙げられる。 Although the alcohol added to a composition is not specifically limited, The following are mentioned specifically.
(Aromatic alcohol)
Examples of the aromatic alcohol include benzyl alcohol, salicyl alcohol, diphenylmethanol, and vanillyl alcohol.
（脂肪族アルコール）
　脂肪族アルコールとしては、例えば、炭素数１であるメタノール；炭素数２であるエタノール；炭素数３である１－プロパノール及び２－プロパノール；炭素数４である１－ブタノール、２－ブタノール、イソブタノール及びｔ－ブタノール；炭素数５である１－ペンタノール、２－ペンタノール、３－ペンタノール、２－メチル－１－ブタノール、３－メチル－１－ブタノール及び２－エチル－１－プロパノール；炭素数６である１－ヘキサノール、２－ヘキサノール、３－ヘキサノール、２－メチル－１－ペンタノール、３－メチル－１－ペンタノール、３－メチル－２－ペンタノール、２－メチル－３－ペンタノール、２－エチル－１－ブタノール、３－エチル－２－ブタノール、２，３－ジメチル－１－ブタノール及びシクロヘキサノール；炭素数７である１－ヘプタノール、２－ヘプタノール、３－ヘプタノール、４－ヘプタノール、２－メチル－１－ヘキサノール、２－メチル－３－ヘキサノール、２－メチル－４－ヘキサノール、３－メチル－１－ヘキサノール、３－メチル―２－ヘキサノール、３－メチル－４－ヘキサノール、２－エチル－１－ペンタノール、２－エチル－３－ペンタノール、２，２－ジメチル－１－ペンタノール、２，３－ジメチル－１－ペンタノール及び２，４－ジメチル－１－ペンタノール；炭素数８である１－オクタノール、２－オクタノール、３－オクタノール、４－オクタノール、２－メチル－１－ヘプタノール、２－メチル－３－ヘプタノール、２－メチル－４－ヘプタノール、２－エチル－１－ヘキサノール、２－エチル－３－ヘキサノール、２－エチル－４－ヘキサノール、２－プロピル－１－ペンタノール、２－プロピル－３－ペンタノール、２－プロピル－４－ペンタノール、２，３－ジメチル－１－ヘキサノール及び２，４－ジメチル－１－ヘキサノール；炭素数９である１－ノナノール、２－ノナノール、３－ノナノール、４－ノナノール、５－ノナノール、２－メチル－１－オクタノール、２－メチル－３－オクタノール、２－メチル－４－オクタノール、２－メチル－５－オクタノール、２－メチル－６－オクタノール、２－エチル－１－ヘプタノール、２－エチル－３－ヘプタノール、２－エチル－４－ヘプタノール、２－エチル－５－ヘプタノール、２，６－ジメチル－１－ヘプタノール、２，６－ジメチル－４－ヘプタノール、３，５，５－トリメチル－１－ヘキサノール、３，５，５－トリメチル－２－ヘキサノール及び２，２，４－トリメチル－１－ヘキサノール；炭素数１０である１－デカノール、２－デカノール、３－デカノール、４－デカノール、５－デカノール、２－メチル－１－ノナノール、２－メチル－３－ノナノール、２－メチル－４－ノナノール、２－メチル－５－ノナノール、２－エチル－１－オクタノール、２－エチル－３－オクタノール、２－エチル－４－オクタノール及び２－エチル－５－オクタノール；炭素数１１である１－ウンデカノール、２－ウンデカノール、３－ウンデカノール、４－ウンデカノール、２－メチルー１－デカノール、２－エチル－１－ノナノール及び２－プロピル－１－オクタノール；炭素数１２である１－ドデカノール、２―ドデカノール、３－ドデカノール、１－エチル－１－デカノール、２－エチル－１－デカノール、３－エチル－１－デカノール及び２－ブチル－１－オクタノール；炭素数１３である１－トリデカノール、２―トリデカノール、３－トリデカノール、１－エチル－１－ウンデカノール、２－エチル－１－ウンデカノール、３－エチルー１－ウンデカノール及び２－ブチル－１－ノナノール；炭素数１４である１－テトラデカノール、２－テトラデカノール、３－テトラデカノール、２－メチル－１－トリデカノール、２－エチル－１－ドデカノール及び２－プロピル－１－ウンデカノール；炭素数１５である１－ペンタデカノール、２－ペンタデカノール、３－ペンタデカノール、２－メチル－１－テトラデカノール、２－エチル－１－トリデカノール及び２－プロピル－１－ドデカノール；炭素数１６である１－ヘキサデカノール、２－ヘキサデカノール、３－ヘキサデカノール、２－メチル－１－ペンタデカノール、２－エチル－１－テトラデカノール及び２－プロピル－１－トリデカノール；炭素数１７である１－ヘプタデカノール、２－ヘプタデカノール、３－ヘプタデカノール、２－メチル－１－ヘキサデカノール、２－エチル－１－ペンタデカノール及び２－プロピル－１－テトラデカノール；炭素数１８である１－オクタデカノール、２－オクタデカノール、３－オクタデカノール、２－メチル－１－ヘプタデカノール、２－エチル－１－ヘキサデカノール及び２－プロピル－１－ペンタデカノール；炭素数１９である１－ノナデカノール、２－ノナデカノール、３－ノナデカノール、２－メチル－１－オクタデカノール、２－エチル－１－ヘプタデカノール及び２－プロピル－１－ヘキサデカノール；炭素数２０である１－エイコサノール、２－エイコサノール、３－エイコサノール、２－メチル－１－ノナデカノール、２－エチル－１－オクタデカノール及び２－プロピル－１－ヘプタデカノール；等が挙げられる。 (Aliphatic alcohol)
Examples of the aliphatic alcohol include methanol having 1 carbon; ethanol having 2 carbons; 1-propanol and 2-propanol having 3 carbons; 1-butanol, 2-butanol and isobutanol having 4 carbons. 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol and 2-ethyl-1-propanol having 5 carbon atoms; carbon 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pen which are the number 6 Tanol, 2-ethyl-1-butanol, 3-ethyl-2-butanol, 2,3-dimethyl-1-butanol and cyclohexa 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-1-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol having 3 carbon atoms, 3- Methyl-1-hexanol, 3-methyl-2-hexanol, 3-methyl-4-hexanol, 2-ethyl-1-pentanol, 2-ethyl-3-pentanol, 2,2-dimethyl-1-pentanol 2,3-dimethyl-1-pentanol and 2,4-dimethyl-1-pentanol; 1-octanol, 2-octanol, 3-octanol, 4-octanol and 2-methyl-1- having 8 carbon atoms Heptanol, 2-methyl-3-heptanol, 2-methyl-4-heptanol, 2-ethyl-1-hexanol, 2-ethyl-3- Xanol, 2-ethyl-4-hexanol, 2-propyl-1-pentanol, 2-propyl-3-pentanol, 2-propyl-4-pentanol, 2,3-dimethyl-1-hexanol and 2,4 -Dimethyl-1-hexanol; 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-methyl-1-octanol, 2-methyl-3-octanol, 2-carbon having 9 carbon atoms Methyl-4-octanol, 2-methyl-5-octanol, 2-methyl-6-octanol, 2-ethyl-1-heptanol, 2-ethyl-3-heptanol, 2-ethyl-4-heptanol, 2-ethyl- 5-heptanol, 2,6-dimethyl-1-heptanol, 2,6-dimethyl-4-heptanol, 3,5,5-trime Cyl-1-hexanol, 3,5,5-trimethyl-2-hexanol and 2,2,4-trimethyl-1-hexanol; 1-decanol, 2-decanol, 3-decanol and 4-decanol having 10 carbon atoms , 5-decanol, 2-methyl-1-nonanol, 2-methyl-3-nonanol, 2-methyl-4-nonanol, 2-methyl-5-nonanol, 2-ethyl-1-octanol, 2-ethyl-3 -Octanol, 2-ethyl-4-octanol and 2-ethyl-5-octanol; 1-undecanol, 2-undecanol, 3-undecanol, 4-undecanol, 2-methyl-1-decanol, 2-ethyl having 11 carbon atoms 1-nonanol and 2-propyl-1-octanol; 1-dodecanol, 2-dos having 12 carbons Canol, 3-dodecanol, 1-ethyl-1-decanol, 2-ethyl-1-decanol, 3-ethyl-1-decanol and 2-butyl-1-octanol; 1-tridecanol having 2 to 13 carbon atoms, 2-tridecanol 3-tridecanol, 1-ethyl-1-undecanol, 2-ethyl-1-undecanol, 3-ethyl-1-undecanol and 2-butyl-1-nonanol; 1-tetradecanol having 14 carbon atoms, 2-tetra Decanol, 3-tetradecanol, 2-methyl-1-tridecanol, 2-ethyl-1-dodecanol and 2-propyl-1-undecanol; 1-pentadecanol having 15 carbon atoms, 2-pentadecanol, 3-pentadecanol, 2-methyl-1-tetradecanol, 2-ethyl-1-tride 1-hexadecanol, 2-hexadecanol, 3-hexadecanol, 2-methyl-1-pentadecanol, 2-ethyl-1-tetra having 16 carbon atoms Decanol and 2-propyl-1-tridecanol; those having 17 carbon atoms, 1-heptadecanol, 2-heptadecanol, 3-heptadecanol, 2-methyl-1-hexadecanol, 2-ethyl-1- Pentadecanol and 2-propyl-1-tetradecanol; 18-carbon 1-octadecanol, 2-octadecanol, 3-octadecanol, 2-methyl-1-heptadecanol, 2-ethyl 1-hexadecanol and 2-propyl-1-pentadecanol; 19-carbon 1-nonadecanol, 2-nonadecanol, 3-no Nadecanol, 2-methyl-1-octadecanol, 2-ethyl-1-heptadecanol and 2-propyl-1-hexadecanol; 1-eicosanol, 2-eicosanol, 3-eicosanol having 20 carbon atoms, 2 -Methyl-1-nonadecanol, 2-ethyl-1-octadecanol and 2-propyl-1-heptadecanol; and the like.
（グリコールモノエーテル系アルコール）
　グリコールモノエーテル系アルコールとしては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等が挙げられる。 (Glycol monoether alcohol)
Examples of the glycol monoether alcohol include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
　ポリイミド前駆体やポリイミドを含む組成物を基体に塗布等を行い、加熱及び／又は乾燥することによりフィルムを得る場合、得られるフィルムが、塗布等のフィルムを形成する環境の影響を受けやすい傾向にある。特に湿度が高い環境で塗布等を行うと、乾燥前の吸湿によって組成物の溶解性が下がり、ポリイミド前駆体やポリイミドが析出し、フィルムが白くなる（白化）場合がある。また、白化が起こったフィルムに対して乾燥や加熱を行っても、耐熱性及び機械特性等の本来のポリイミドの特性が得られないという問題点がある。これらを解決するために、溶媒としては、エーテル系溶媒、ケトン系溶媒、アミド系溶媒、スルホン系溶媒、複素環系溶媒、フェノール系溶媒、ラクトン系溶媒及びエステル系溶媒からなる群より選ばれる１種以上であり、且つ、２０℃における蒸気圧が５００００Ｐａ以下である溶媒（以下、溶媒Ａと表すことがある。）、並びにアルコール（以下、溶媒Ｂと表すことがある）を用いてもよい。溶媒Ａ及び溶媒Ｂを含むことで白化が抑制できるのは、組成物全体の疎水性が上がり、吸湿が抑制されるためと推測される。
　溶媒Ｂは、芳香族アルコール、脂肪族アルコール及びグリコールモノエーテル系アルコールからなる群より選ばれる１種以上であることが好ましい。これらの溶媒は、単独で用いてもよく、任意の割合で併用してもよい。
　中でも、ポリイミド前駆体の溶解性が高くなるため、脂肪族アルコール又はグリコールモノエーテル系アルコールが好ましく、特に、脂肪族アルコールが好ましい。
　脂肪族アルコールの中でも、炭素数が４以上であることが好ましく、炭素数が５以上であることがより好ましい。また２０以下であることが好ましく、１５以下であることが更に好ましい。
　また、脂肪族アルコールの中でも、環状及び分岐を有することが好ましく、分岐の場合、分岐位置がβ及び/又はγ位であることが特に好ましい。
　上記のように適当な炭素数及び/又は置換位置を有することで、ポリイミド前駆体の溶解性が高くなる傾向にある。 When a film is obtained by applying a polyimide precursor or a polyimide-containing composition to a substrate and heating and / or drying, the resulting film tends to be easily affected by the environment in which the film is formed. is there. In particular, when coating or the like is performed in an environment with high humidity, the solubility of the composition decreases due to moisture absorption before drying, and a polyimide precursor or polyimide may be deposited, resulting in whitening (whitening) of the film. Further, there is a problem in that original polyimide characteristics such as heat resistance and mechanical characteristics cannot be obtained even if drying or heating is performed on a film that has been whitened. In order to solve these problems, the solvent is selected from the group consisting of ether solvents, ketone solvents, amide solvents, sulfone solvents, heterocyclic solvents, phenol solvents, lactone solvents, and ester solvents. A solvent having a vapor pressure at 20 ° C. of 50000 Pa or less (hereinafter sometimes referred to as solvent A) and an alcohol (hereinafter sometimes referred to as solvent B) may be used. The reason why whitening can be suppressed by including the solvent A and the solvent B is presumed to be because the hydrophobicity of the entire composition is increased and moisture absorption is suppressed.
The solvent B is preferably at least one selected from the group consisting of aromatic alcohols, aliphatic alcohols, and glycol monoether alcohols. These solvents may be used alone or in combination at any ratio.
Especially, since the solubility of a polyimide precursor becomes high, aliphatic alcohol or glycol monoether type | system | group alcohol is preferable, and especially aliphatic alcohol is preferable.
Among aliphatic alcohols, the number of carbon atoms is preferably 4 or more, and more preferably 5 or more. Moreover, it is preferable that it is 20 or less, and it is still more preferable that it is 15 or less.
Further, among the aliphatic alcohols, it is preferable to have a ring and a branch, and in the case of a branch, the branch position is particularly preferably a β and / or γ position.
By having an appropriate carbon number and / or substitution position as described above, the solubility of the polyimide precursor tends to increase.
　溶媒Ａ及び溶媒Ｂの蒸気圧差は特に制限はないが、好ましくは１００００Ｐａ以下、より好ましくは５０００Ｐａ以下、さらに好ましくは１０００Ｐａ以下である。また、下限は無く、蒸気圧差はゼロでもよい。さらに、溶媒Ａ及び溶媒Ｂの蒸気圧はどちらが高くてもよい。
　蒸気圧差が特定の範囲であることで、塗布等の膜形成時のポリイミド前駆体組成物の濃度変化が少なくなり、そのため、白化抑制、膜中成分の均一性、及び膜の平滑性に優れた膜が得られる傾向にある。さらに、膜の乾燥後や加熱後の膜中の残留溶媒が少なくなる傾向にある。 The vapor pressure difference between the solvent A and the solvent B is not particularly limited, but is preferably 10,000 Pa or less, more preferably 5000 Pa or less, and still more preferably 1000 Pa or less. There is no lower limit, and the vapor pressure difference may be zero. Further, either the solvent A or the solvent B may have a higher vapor pressure.
When the vapor pressure difference is in a specific range, the concentration change of the polyimide precursor composition during film formation such as coating is reduced. Therefore, it is excellent in whitening suppression, uniformity of components in the film, and film smoothness. A film tends to be obtained. Further, the residual solvent in the film after drying or heating tends to decrease.
　溶媒Ａ及び溶媒Ｂの沸点差は特に制限はないが、好ましくは１００℃以下、より好ましくは８０℃以下、さらに好ましくは５０℃以下である。また、下限は無く、沸点差はゼロでもよい。さらに、溶媒Ａ及び溶媒Ｂの沸点はどちらが高くてもよい。
　沸点差が特定の範囲であることで、膜形成時のポリイミド前駆体組成物の濃度変化が少なくなり、そのため、白化抑制、膜中成分の均一性及び膜の平滑性に優れた膜が得られる傾向にある。さらに、膜の乾燥後や加熱後の膜中の残留溶媒が少なくなる傾向にある。 The difference in boiling point between the solvent A and the solvent B is not particularly limited, but is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 50 ° C. or lower. There is no lower limit, and the boiling point difference may be zero. Further, either of the boiling points of the solvent A and the solvent B may be higher.
When the difference in boiling point is within a specific range, the concentration change of the polyimide precursor composition during film formation is reduced, and thus a film excellent in whitening suppression, uniformity of components in the film and film smoothness can be obtained. There is a tendency. Further, the residual solvent in the film after drying or heating tends to decrease.
　溶媒Ａ及び溶媒Ｂの全溶媒に対する割合の比は特に制限はないが、溶媒Ａに対して、溶媒Ｂは、５０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。また、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１．０質量％以上がさらに好ましい。溶媒Ａ及び溶媒Ｂの割合の比がこの範囲であることで、ポリイミド前駆体の溶解性を維持し、かつ、白化抑制効果が得られる傾向にある。 The ratio of the ratio of the solvent A and the solvent B to the total solvent is not particularly limited. preferable. Moreover, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1.0 mass% or more is further more preferable. When the ratio of the ratio of the solvent A and the solvent B is within this range, the solubility of the polyimide precursor is maintained and the whitening suppression effect tends to be obtained.
　上記溶媒を用いて形成されたフィルムは、特に透明性や低着色性に優れるため、コーティング材料、表面保護層、接着剤、デバイス用基板及び絶縁膜等の用途に好適に用いることができる。 Since the film formed using the above solvent is particularly excellent in transparency and low colorability, it can be suitably used for applications such as coating materials, surface protective layers, adhesives, device substrates and insulating films.
（組成物の粘度）
　本発明の組成物の粘度は特に制限はないが、２５℃における濃度２０％の粘度で通常２００ｃＰ以上、好ましくは３００ｃＰ以上、さらに好ましくは５００ｃＰ以上であり、通常２０００００ｃＰ以下、好ましくは１０００００ｃＰ以下、さらに好ましくは８００００ｃＰ以下である。組成物の粘度がこの範囲であることで、製造時の取り扱いがしやすくなり、また製膜時に膜厚が均一になりやすい傾向にある。
　組成物の粘度は、従来知られている方法で測定することができる。例えば、振動式粘度計、Ｅ型粘度計等を用いることができる。 (Viscosity of composition)
The viscosity of the composition of the present invention is not particularly limited, but is usually 200 cP or more, preferably 300 cP or more, more preferably 500 cP or more at a viscosity of 20% at 25 ° C., usually 200000 cP or less, preferably 100000 cP or less, Preferably it is 80,000 cP or less. When the viscosity of the composition is within this range, it is easy to handle during production, and the film thickness tends to be uniform during film formation.
The viscosity of the composition can be measured by a conventionally known method. For example, a vibration type viscometer, an E type viscometer, or the like can be used.
（組成物の濃度）
　本発明の組成物に含まれるポリイミド前駆体及び／又はポリイミドの濃度は、特に制限はないが、通常３質量％以上、好ましくは５質量％以上、さらに好ましくは７質量％以上であり、通常６０質量％以下、好ましくは５０質量％以下、さらに好ましくは４５質量％以下である。濃度がこの範囲であることで、製造が容易となり、また製膜時に膜厚が均一になりやすい傾向にある。
　組成物の濃度は従来知られている方法で測定することができる。例えば、前述の方法で求めることができる。 (Concentration of composition)
The concentration of the polyimide precursor and / or polyimide contained in the composition of the present invention is not particularly limited, but is usually 3% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, and usually 60%. It is not more than mass%, preferably not more than 50 mass%, more preferably not more than 45 mass%. When the concentration is within this range, the production becomes easy, and the film thickness tends to be uniform during film formation.
The concentration of the composition can be measured by a conventionally known method. For example, it can be determined by the method described above.
（組成物に含まれるポリイミドの製造）
　組成物に含まれるポリイミドの製造方法は、特段制限はない。例えば、ポリイミド前駆体を製造しポリイミドを得る方法、テトラカルボン酸二無水物とジアミン化合物から直接ポリイミドを製造する方法等を用いることができる。 (Production of polyimide contained in the composition)
There is no particular limitation on the method for producing the polyimide contained in the composition. For example, the method of manufacturing a polyimide precursor and obtaining a polyimide, the method of manufacturing a polyimide directly from tetracarboxylic dianhydride and a diamine compound, etc. can be used.
（ポリイミド前駆体から製造する方法）
　前記の方法等で得られたポリイミド前駆体を溶媒存在下で脱水環化することにより、ポリイミドを得ることができる。イミド化は従来知られている任意の方法を用いて行うことができるが、例えば熱的に環化させる加熱イミド化、化学的に環化させる化学イミド化等が挙げられる。これらのイミド化反応は単独で行っても、複数組み合わせて行ってもよい。 (Method of manufacturing from polyimide precursor)
A polyimide can be obtained by dehydrating and cyclizing the polyimide precursor obtained by the above method in the presence of a solvent. Although imidation can be performed using any conventionally known method, for example, thermal imidization for thermal cyclization, chemical imidization for chemical cyclization, and the like can be given. These imidation reactions may be performed alone or in combination.
（加熱イミド化）
　ポリイミド前駆体をイミド化する際の溶媒は、前記のポリイミド前駆体を得る反応時に使用した溶媒と同様のものが挙げられる。ポリイミド前駆体製造時の溶媒と、ポリイミド製造時の溶媒は同じものを用いても、異なるものを用いてもよい。
　この場合、イミド化によって生じた水は閉環反応を阻害するため、系外に排出してもよい。イミド化反応時のポリイミド前駆体の濃度は特に制限はないが、通常１質量％以上、好ましくは５質量％以上であり、通常７０質量％以下、好ましくは４０質量％以下である。この範囲で行うことによって、生産効率が高く、また製造しやすい溶液粘度で製造することができる傾向にある。 (Heat imidization)
Examples of the solvent for imidizing the polyimide precursor include the same solvents as those used in the reaction for obtaining the polyimide precursor. The solvent at the time of manufacturing the polyimide precursor and the solvent at the time of manufacturing the polyimide may be the same or different.
In this case, water generated by imidization may be discharged out of the system in order to inhibit the ring closure reaction. The concentration of the polyimide precursor during the imidation reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. By carrying out in this range, the production efficiency tends to be high and the solution viscosity tends to be easy to produce.
　イミド化反応温度は特に制限されないが、通常５０℃以上、好ましくは８０℃以上、さらに好ましくは１００℃以上であり、通常３００℃以下、好ましくは２８０℃以下、より好ましくは２５０℃以下である。この範囲で行うことで、イミド化反応が効率よく進行し、イミド化反応以外の反応が抑制される傾向にあるため好ましい。
　反応時の圧力は常圧、加圧、減圧のいずれでもよい。雰囲気は、空気下でも不活性雰囲気下でもよい。 The imidation reaction temperature is not particularly limited, but is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. Performing in this range is preferable because the imidization reaction proceeds efficiently and reactions other than the imidization reaction tend to be suppressed.
The pressure during the reaction may be normal pressure, pressurization, or reduced pressure. The atmosphere may be air or an inert atmosphere.
　また、イミド化を促進するイミド化促進剤として、求核性、求電子性を高める働きをもつ化合物を加えることもできる。具体的には、例えば、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、トリエチレンジアミン、Ｎ－メチルピロリジン、Ｎ－エチルピロリジン、Ｎ－メチルピペリジン、Ｎ－エチルピペリジン、イミダゾール、ピリジン、キノリン、イソキノリン等の三級アミン化合物；４－ヒドロキシフェニル酢酸、３－ヒドロキシ安息香酸、Ｎ－アセチルグリシン、Ｎ－ベンゾイルグリシン等のカルボン酸化合物；３，５－ジヒドロキシアセトフェノン、３，５－ジヒドロキシ安息香酸メチル、ピロガロール、メチルガレート、エチルガレート、ナフタレン－１，６－ジオール等の多価フェノール化合物；２－ヒドロキシピリジン、３－ヒドロキシピリジン、４－ヒドロキシピリジン、４－ピリジンメタノール、Ｎ，Ｎ－ジメチルアミノピリジン、ニコチンアルデヒド、イソニコチンアルデヒド、ピコリンアルデヒド、ピコリンアルデヒドオキシム、ニコチンアルデヒドオキシム、イソニコチンアルデヒドオキシム、ピコリン酸エチル、ニコチン酸エチル、イソニコチン酸エチル、ニコチンアミド、イソニコチンアミド、２－ヒドロキシニコチン酸、２，２’－ジピリジル、４，４’－ジピリジル、３－メチルピリダジン、キノリン、イソキノリン、フェナントロリン、１，１０－フェナントロリン、イミダゾール、ベンズイミダゾール、１，２，４－トリアゾール等の複素環化合物；等が挙げられる。 Further, as an imidization accelerator for promoting imidization, a compound having a function of enhancing nucleophilicity and electrophilicity can be added. Specifically, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine , Tertiary amine compounds such as N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline and isoquinoline; carboxylic acids such as 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, N-acetylglycine and N-benzoylglycine Compound; Polyhydric phenol compound such as methyl 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, pyrogallol, methyl gallate, ethyl gallate, naphthalene-1,6-diol; 2-hydroxy Lysine, 3-hydroxypyridine, 4-hydroxypyridine, 4-pyridinemethanol, N, N-dimethylaminopyridine, nicotinaldehyde, isonicotialdehyde, picolinaldehyde, picolinaldehyde oxime, nicotinaldehyde oxime, isonicotialdehyde oxime, picolinic acid Ethyl, ethyl nicotinate, ethyl isonicotinate, nicotinamide, isonicotinamide, 2-hydroxynicotinic acid, 2,2'-dipyridyl, 4,4'-dipyridyl, 3-methylpyridazine, quinoline, isoquinoline, phenanthroline, 1 , 10-phenanthroline, imidazole, benzimidazole, 1,2,4-triazole and other heterocyclic compounds;
　これらの中で、三級アミン化合物又は複素環化合物が好ましく、トリエチルアミン、イミダゾール又はピリジンが、イミド化率を制御しやすい傾向があるためより好ましい。これらの化合物は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 Among these, tertiary amine compounds or heterocyclic compounds are preferable, and triethylamine, imidazole, or pyridine is more preferable because it tends to control the imidation rate. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
　イミド化促進剤の使用量は、カルボキシル基又はエステル基に対して、通常０．０１ｍｏｌ％以上であり、０．１ｍｏｌ％以上が好ましく、１ｍｏｌ％以上が更に好ましい。また、５０ｍｏｌ％以下であることが好ましく、１０ｍｏｌ％以下であることがより好ましい。触媒の使用量がこのような範囲にあることにより、イミド化反応が効率よく進行し、且つ、イミド化率を制御したポリイミドを得ることができる傾向にある。
　また、イミド化促進剤を添加するタイミングは、所望のイミド化率にするために適宜調整することができ、加熱開始前でもよく、加熱中でもよい。また複数回に分けて添加してもよい。 The amount of the imidization accelerator used is usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 1 mol% or more based on the carboxyl group or ester group. Moreover, it is preferable that it is 50 mol% or less, and it is more preferable that it is 10 mol% or less. When the usage-amount of a catalyst exists in such a range, it exists in the tendency for the imidation reaction to advance efficiently and to obtain the polyimide which controlled the imidation ratio.
Moreover, the timing which adds an imidation promoter can be adjusted suitably in order to make it a desired imidation rate, may be before a heating start, and may be during a heating. Moreover, you may add in multiple times.
（化学イミド化）
　ポリイミド前駆体を溶媒存在下で、脱水縮合剤を用いて化学的にイミド化することにより、ポリイミドを得ることができる。
　化学イミド化の際に使用する溶媒としては前記のポリイミド前駆体を得る反応時に使用した溶媒と同様のものが挙げられる。 (Chemical imidization)
A polyimide can be obtained by chemically imidizing a polyimide precursor using a dehydration condensing agent in the presence of a solvent.
Examples of the solvent used in the chemical imidization include the same solvents as those used in the reaction for obtaining the polyimide precursor.
　脱水縮合剤としては、例えば、Ｎ，Ｎ－ジシクロヘキシルカルボジイミド、Ｎ，Ｎ－ジフェニルカルボジイミド等のＮ，Ｎ－２置換カルボジイミド；無水酢酸、無水トリフルオロ酢酸等の酸無水物；塩化チオニル、塩化トシル等の塩化物；アセチルクロライド、アセチルブロマイド、プロピオニルアイオダイド、アセチルフルオライド、プロピオニルクロライド、プロピオニルブロマイド、プロピオニルアイオダイド、プロピオニルフルオライド、イソブチリルクロライド、イソブチリルブロマイド、イソブチリルアイオダイド、イソブチリルフルオライド、ｎ－ブチリルクロライド、ｎ－ブチリルブロマイド、ｎ－ブチリルアイオダイド、ｎ－ブチリルフルオライド、モノ－，ジ－，トリ－クロロアセチルクロライド、モノ－，ジ－，トリ－ブロモアセチルクロライド、モノ－，ジ－，トリ－アイオドアセチルクロライド、モノ－，ジ－，トリ－フルオロアセチルクロライド、無水クロロ酢酸、フェニルホスフォニックジクロライド、チオニルクロライド、チオニルブロマイド、チオニルアイオダイド、チオニルフルオライド等のハロゲン化化合物；三塩化リン、亜リン酸トリフェニル、ジエチルリン酸シアニド等のリン化合物；等が挙げられる。 Examples of the dehydrating condensing agent include N, N-2-substituted carbodiimides such as N, N-dicyclohexylcarbodiimide and N, N-diphenylcarbodiimide; acid anhydrides such as acetic anhydride and trifluoroacetic anhydride; thionyl chloride and tosyl chloride and the like. Chlorides of: acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobuty Ryl fluoride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di-, to -Bromoacetyl chloride, mono-, di-, tri-iodoacetyl chloride, mono-, di-, tri-fluoroacetyl chloride, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyl iodide, thionyl Halogenated compounds such as fluoride; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite and diethyl phosphate cyanide; and the like.
　これらの中で、酸無水物及びハロゲン化化合物が好ましく、特に、酸無水物が、イミド化反応が効率よく進行し、且つ、イミド化率を制御したポリイミドを得ることができる傾向にあるためより好ましい。これらの化合物は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 Among these, acid anhydrides and halogenated compounds are preferable, and in particular, acid anhydrides tend to allow the imidization reaction to proceed efficiently and to obtain a polyimide with a controlled imidization rate. preferable. These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
　これらの脱水縮合剤の使用量は、ポリイミド前駆体１ｍｏｌに対して、通常０．１ｍｏｌ以上、好ましくは０．２ｍｏｌ以上であり、通常１．０ｍｏｌ以下、好ましくは０．９ｍｏｌ以下である。脱水縮合剤をこの範囲とすることで、イミド化率を制御することができる。 The amount of these dehydrating condensing agents to be used is usually 0.1 mol or more, preferably 0.2 mol or more, usually 1.0 mol or less, preferably 0.9 mol or less with respect to 1 mol of the polyimide precursor. By setting the dehydration condensing agent within this range, the imidization rate can be controlled.
　イミド化反応時のポリイミド前駆体の濃度に特に制限はないが、通常１質量％以上、好ましくは５質量％以上であり、通常７０質量％以下、好ましくは４０質量％以下である。この範囲とすることで、イミド化率を制御でき、生産効率が高く、また製造しやすい溶液粘度で製造することができる傾向にある。 Although there is no restriction | limiting in particular in the density | concentration of the polyimide precursor at the time of imidation reaction, Usually, 1 mass% or more, Preferably it is 5 mass% or more, and is 70 mass% or less normally, Preferably it is 40 mass% or less. By setting it within this range, the imidation rate can be controlled, production efficiency tends to be high, and the solution viscosity tends to be easy to manufacture.
　イミド化反応温度は特に制限されないが、通常０℃以上、好ましくは１０℃以上、さらに好ましくは２０℃以上であり、通常１５０℃以下、好ましくは１３０℃以下、さらに好ましくは１００℃以下である。この範囲で行うことで、イミド化反応が効率よく進行し、且つ、イミド化率を制御したポリイミドを得ることができる傾向にあるため好ましい。さらに、イミド化反応以外の副反応が抑制されるため好ましい。
　反応時の圧力は常圧、加圧又は減圧のいずれでもよい。雰囲気は、空気下でも不活性雰囲気下でもよい。 The imidation reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and is usually 150 ° C. or lower, preferably 130 ° C. or lower, more preferably 100 ° C. or lower. It is preferable to carry out in this range since the imidization reaction proceeds efficiently and a polyimide having a controlled imidization rate tends to be obtained. Furthermore, it is preferable because side reactions other than the imidization reaction are suppressed.
The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.
　また、イミド化を促進する触媒として、前記の三級アミン類等を加熱イミド化と同様に加えることもできる。 Also, as a catalyst for promoting imidization, the above-mentioned tertiary amines can be added in the same manner as in the heating imidization.
（テトラカルボン酸二無水物とジアミン化合物からポリイミドを製造する方法）
　テトラカルボン酸二無水物とジアミン化合物から、従来既知の方法を用いて、直接ポリイミドを得ることができる。この方法はポイミド前駆体の合成からイミド化を、反応の停止や前駆体の単離を経ることなく、イミド化までを行うものである。 (Method for producing polyimide from tetracarboxylic dianhydride and diamine compound)
A polyimide can be directly obtained from a tetracarboxylic dianhydride and a diamine compound using a conventionally known method. This method performs imidization from synthesis of a poimide precursor to imidization without stopping the reaction or isolating the precursor.
　テトラカルボン酸二無水物とジアミン化合物の添加順序や添加方法には特に限定はないが、例えば、溶媒にテトラカルボン酸二無水物とジアミン化合物を順に投入し、イミド化までの反応が進行する温度で撹拌することでポリイミドが得られる。 There are no particular limitations on the order and method of addition of tetracarboxylic dianhydride and diamine compound. For example, the temperature at which the reaction until imidization proceeds by sequentially adding tetracarboxylic dianhydride and diamine compound to the solvent. The polyimide is obtained by stirring at.
　ジアミン化合物の量は、テトラカルボン酸二無水物１ｍｏｌに対して、通常０．７ｍｏｌ以上、好ましくは０．８ｍｏｌ以上であり、通常１．３ｍｏｌ以下、好ましくは１．２ｍｏｌ以下である。ジアミン化合物の量をこのような範囲とすることにより、イミド化率を制御したポリイミドを得ることができ、得られるポリイミド組成物の収率が向上する傾向にある。 The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. By setting the amount of the diamine compound in such a range, it is possible to obtain a polyimide with a controlled imidation rate, and the yield of the resulting polyimide composition tends to be improved.
　溶媒中のテトラカルボン酸二無水物とジアミン化合物の濃度は、各々の条件や重合中の粘度に対して適宜設定しうるが、テトラカルボン酸二無水物とジアミン化合物の合計質量は、特段の設定ないが、全液量に対し、通常１質量％以上、好ましくは５質量％以上であり、通常７０質量％以下、好ましくは４０質量％以下である。溶媒中の濃度が適当な範囲であることで、分子量の伸長が起こりやすくなり、また、撹拌も容易となる傾向にある。 The concentration of tetracarboxylic dianhydride and diamine compound in the solvent can be set as appropriate for each condition and viscosity during polymerization, but the total mass of tetracarboxylic dianhydride and diamine compound is a special setting. However, it is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less, based on the total liquid amount. When the concentration in the solvent is within an appropriate range, elongation of molecular weight tends to occur, and stirring tends to be facilitated.
　この反応で用いる溶媒としては、前記のポリイミド前駆体を得る反応時に使用した溶媒と同様のものが挙げられる。
　また、テトラカルボン酸二無水物とジアミン化合物からポリイミドを得る場合も、ポリイミド前駆体からポリイミドを得る場合と同様に、加熱イミド化及び／又は化学イミド化を用いることができる。この場合の加熱イミド化や化学イミド化の反応条件等は、前記と同様である。 Examples of the solvent used in this reaction include the same solvents as those used in the reaction for obtaining the polyimide precursor.
Moreover, also when obtaining a polyimide from a tetracarboxylic dianhydride and a diamine compound, heating imidation and / or chemical imidation can be used similarly to the case where a polyimide is obtained from a polyimide precursor. The reaction conditions for heating imidization and chemical imidization in this case are the same as described above.
（組成物に含まれるポリイミドの再沈再溶解）
　得られたポリイミドは、そのままポリイミド組成物として用いてもよく、また貧溶媒中に添加することでポリイミドを固体状に析出させた後に、他の溶媒に再溶解させてポリイミド組成物として用いることもできる。 (Reprecipitation and re-dissolution of polyimide contained in the composition)
The obtained polyimide may be used as it is as a polyimide composition, or may be added to a poor solvent to precipitate the polyimide in a solid state, and then re-dissolved in another solvent to be used as a polyimide composition. it can.
　この時の貧溶媒は特に制限はなく、ポリイミドの種類によって適宜選択しうるが、例えば、ジエチルエーテル、ジイソプロピルエーテル等のエーテル系溶媒；アセトン、メチルエチルケトン、イソブチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、イソプロピルアルコール等のアルコール系溶媒；等が挙げられる。中でも、イソプロピルアルコール等のアルコール系溶媒が効率よく析出物が得られ、沸点が低く乾燥が容易となる傾向にあるため好ましい。これらの溶媒は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 The poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of polyimide. For example, ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; And alcohol solvents such as methanol, ethanol, isopropyl alcohol, and the like. Among them, alcohol solvents such as isopropyl alcohol are preferable because precipitates can be obtained efficiently and the boiling point is low and the drying tends to be easy. These solvents may be used alone or in combination of two or more in any ratio and combination.
　また、ポリイミドを再溶解させる溶媒としては、例えば、ヘキサン、シクロヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、メシチレン、アニソール等の炭化水素系溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド系溶媒；ジメチルスルホキシド等の非プロトン系溶媒；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系溶媒；等が挙げられる。この中でも特にアニソール、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、エチレングリコールジメチルエーテル、及びエチレングリコールモノメチルエーテルが好ましい。これらの溶媒は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。 Examples of the solvent for re-dissolving polyimide include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, and anisole; N, N-dimethylformamide, N, N-dimethylacetamide, N An amide solvent such as methyl-2-pyrrolidone; an aprotic solvent such as dimethyl sulfoxide; a glycol solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; Etc. Of these, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether, and ethylene glycol monomethyl ether are particularly preferable. These solvents may be used alone or in combination of two or more in any ratio and combination.
　本発明の組成物には本発明の主旨を逸脱しない限りその他の溶媒を含んでもよい。その種類は特に限定されないが、塗工性が良くなるためアルコールが好ましい。好ましいアルコールは前述のものと同様である。 The composition of the present invention may contain other solvents without departing from the gist of the present invention. The type is not particularly limited, but alcohol is preferred because of good coatability. Preferred alcohols are the same as those described above.
　本発明の組成物には、被塗布体との接着性を調節するため、シランカップリング剤、チタンカップリング剤等のカップリング剤を添加することができる。 In the composition of the present invention, a coupling agent such as a silane coupling agent or a titanium coupling agent can be added in order to adjust the adhesion to the coated body.
　シランカップリング剤としては、例えば、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリプロポキシシラン、γ－アミノプロピルトリブトキシシラン、γ－アミノエチルトリエトキシシラン、γ－アミノエチルトリメトキシシラン、γ－アミノエチルトリプロポキシシラン、γ－アミノエチルトリブトキシシラン、γ－アミノブチルトリエトキシシラン、γ－アミノブチルトリメトキシシラン、γ－アミノブチルトリプロポキシシラン、γ－アミノブチルトリブトキシシラン等が挙げられる。 Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ -Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-amino Examples include butyltributoxysilane.
　チタンカップリング剤としては、例えば、γ－アミノプロピルトリエトキシチタン、γ－アミノプロピルトリメトキシチタン、γ－アミノプロピルトリプロポキシチタン、γ－アミノプロピルトリブトキシチタン、γ－アミノエチルトリエトキシチタン、γ－アミノエチルトリメトキシチタン、γ－アミノエチルトリプロポキシチタン、γ－アミノエチルトリブトキシチタン、γ－アミノブチルトリエトキシチタン、γ－アミノブチルトリメトキシチタン、γ－アミノブチルトリプロポキシチタン、γ－アミノブチルトリブトキシチタン等が挙げられる。 Examples of the titanium coupling agent include γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, γ-aminopropyltributoxytitanium, γ-aminoethyltriethoxytitanium, γ -Aminoethyltrimethoxytitanium, γ-aminoethyltripropoxytitanium, γ-aminoethyltributoxytitanium, γ-aminobutyltriethoxytitanium, γ-aminobutyltrimethoxytitanium, γ-aminobutyltripropoxytitanium, γ-amino Examples thereof include butyl tributoxy titanium.
　これらのカップリング剤は、１種を単独で用いても、２種以上を任意の比率及び組合せで用いてもよい。このときの使用量は、ポリイミドに対して、０．１質量％以上、３質量％以下が好ましい。 These coupling agents may be used singly or in combination of two or more in any ratio and combination. The amount used at this time is preferably 0.1% by mass or more and 3% by mass or less with respect to the polyimide.
　その他、必要に応じて、各種添加剤を配合することも可能である。例えば本発明の効果を損なわない範囲で、他の粉末状、粒状、板状、繊維状等の無機系充填剤や有機系充填剤を配合することができる。 In addition, various additives can be blended as necessary. For example, other powdery, granular, plate-like, fiber-like inorganic fillers and organic fillers can be blended within a range not impairing the effects of the present invention.
　これら充填剤は不織布等のような平板状に加工したものを用いてもよく、複数を混ぜて用いてもよい。さらに所望に応じ、樹脂組成物に通常用いられている各種添加剤、例えば滑剤、着色剤、安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、難燃剤、可塑剤、離型剤等を配合することができる。これら各種充填剤及び添加成分はポリイミドを製造するどの工程のどの段階で添加してもよい。 These fillers may be processed into a flat shape such as a non-woven fabric or may be used in combination. Furthermore, if desired, various additives commonly used in resin compositions such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers, mold release agents, etc. Can be blended. These various fillers and additive components may be added at any stage of any process for producing polyimide.
（ポリイミド）
　本発明に係るポリイミドは、テトラカルボン酸残及びジアミン残基を含み、テトラカルボン酸残基としてＩＩＩ群から１つ以上選択される部分構造及びＩＶ群から１つ以上選択される部分構造を有し、ジアミン残基として式（１１）で示される部分構造を有するものである。 (Polyimide)
The polyimide according to the present invention contains a tetracarboxylic acid residue and a diamine residue, and has a partial structure selected from group III and one or more partial groups selected from group IV as a tetracarboxylic acid residue. The diamine residue has a partial structure represented by the formula (11).
ＩＩＩ群：下記式（７）及び式（８）を示す。 Group III: The following formula (7) and formula (8) are shown.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
［式（７）において、
Ｘ１は直接結合、アルキレン基、カルボニル基、エーテル結合又はスルホニル基を示す。］ [In Formula (7),
X 1 represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. ]
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
ＩＶ群：下記式（９）及び式（１０）を示す。 Group IV: The following formulas (9) and (10) are shown.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
［式（９）において、
ｎ’及びｍ’は、それぞれ独立に、０又は１を示し、
Ｒ５及びＲ６は、それぞれ独立に、アルキル基、アルケニル基又は芳香環を示す。Ｒ５及びＲ６は、異なっていても同じでもよく、また環を形成していてもよい。］ [In Formula (9),
n ′ and m ′ each independently represent 0 or 1,
R 5 and R 6 each independently represents an alkyl group, an alkenyl group or an aromatic ring. R 5 and R 6 may be different or the same, and may form a ring. ]
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
［式（１０）において、
Ｙ’は、直接結合又は２価の有機基を示す。］ [In Formula (10),
Y ′ represents a direct bond or a divalent organic group. ]
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
［式（１１）において、
Ｒ７及びＲ８は、それぞれ独立に、アルキル基、アルコキシ基、アミノ基又は水酸基を示す。］ [In Formula (11),
R 7 and R 8 each independently represents an alkyl group, an alkoxy group, an amino group or a hydroxyl group. ]
　式（７）のＸ１は、式（１）のＸと同義であり、好ましい範囲及び有していてもよい置換基も同義である。
　式（９）のｎ’及びｍ’は、式（３）のｎ及びｍとそれぞれ同義であり、好ましい範囲も同義である。また、Ｒ５及びＲ６は、式（３）のＲ１及びＲ２とそれぞれ同義であり、好ましい範囲及び有していてもよい置換基も同義である。
　式（１０）のＹ’は、式（４）のＹと同義であり、好ましい範囲及び有していてもよい置換基も同義である。
　式（１１）のＲ７及びＲ８は、式（５）のＲ３及びＲ４とそれぞれ同義であり、好ましい範囲及び有していてもよい置換基も同義である。 X 1 in formula (7) has the same meaning as X in formula (1), and the preferred range and the substituent that may be present are also synonymous.
N ′ and m ′ in the formula (9) have the same meanings as n and m in the formula (3), respectively, and a preferable range is also the same. Moreover, R < 5 > and R < 6 > are synonymous with R < 1 > and R < 2 > of Formula (3), respectively, A preferable range and the substituent which may have are also synonymous.
Y ′ in formula (10) has the same meaning as Y in formula (4), and the preferred range and the substituent that may be present are also synonymous.
R 7 and R 8 in the formula (11) have the same meanings as R 3 and R 4 in the formula (5), respectively, and the preferred range and the substituents that may be included are also the same.
　本発明のポリイミドは、本発明の主旨を逸脱しない範囲で、上記式（７）、式（８）、式（９）及び式（１０）で示される部分構造以外を有するテトラカルボン酸残基を有していてもよい。また、式（１１）で示される部分構造以外を有するジアミン残基を有していてもよい。
　上記式（７）、式（８）、式（９）及び式（１０）で示される部分構造以外を有するテトラカルボン酸残基としては、上記式（１）、式（２）、式（３）及び式（４）で表される部分構造以外を有するテトラカルボン酸残基として示された、芳香族テトラカルボン酸二無水物及び脂肪族テトラカルボン酸二無水物等のテトラカルボン酸二無水物から誘導されるテトラカルボン酸残基が挙げられる。
　上記式（１１）で示される部分構造以外を有するジアミン残基としては、上記式（５）で表される部分構造以外を有するジアミン残基として示されたジアミン化合物から誘導されるジアミン残基が挙げられる。 The polyimide of the present invention has a tetracarboxylic acid residue having a structure other than the partial structure represented by the above formula (7), formula (8), formula (9) and formula (10) without departing from the gist of the present invention. You may have. Moreover, you may have the diamine residue which has other than the partial structure shown by Formula (11).
Examples of the tetracarboxylic acid residue having other than the partial structure represented by the above formula (7), formula (8), formula (9) and formula (10) include the above formula (1), formula (2) and formula (3). ) And tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides, shown as tetracarboxylic acid residues having other than the partial structure represented by formula (4) And tetracarboxylic acid residues derived from.
As the diamine residue having other than the partial structure represented by the above formula (11), a diamine residue derived from a diamine compound represented as a diamine residue having other than the partial structure represented by the above formula (5) Can be mentioned.
　本発明のポリイミドは、屈曲部位を有する、テトラカルボン酸残基及び／又はジアミン残基を有することが、光学特性を向上させる傾向にあるため好ましい。
　屈曲部位を有するテトラカルボン酸及び／又はジアミン残基としては、前記本発明の組成物中のポリイミド前駆体及び／又はポリイミドが有していてもよい屈曲部位を有するテトラカルボン酸及び／又はジアミン残基と同義であり、好ましい範囲も同義である。 The polyimide of the present invention preferably has a tetracarboxylic acid residue and / or a diamine residue having a bent portion, since it tends to improve optical properties.
As the tetracarboxylic acid and / or diamine residue having a bent portion, the tetracarboxylic acid and / or diamine residue having a bent portion which may be included in the polyimide precursor and / or polyimide in the composition of the present invention. It is synonymous with group, and its preferable range is also synonymous.
　式（１１）で表される部分構造以外を有するジアミン残基の中でも、光学特性が向上するため、式（１２）で表される部分構造を有するジアミン残基を有することが好ましい。 Among diamine residues having other than the partial structure represented by formula (11), it is preferable to have a diamine residue having a partial structure represented by formula (12) in order to improve optical properties.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
［式（１２）において、
Ｚ’は直接結合、スルホニル基、アルキレン基、カルボニル基又はエーテル結合を示し、
Ａ’及びＢ’はそれぞれ独立に、直接結合、２価の芳香環、２価の複素環又はフェニルエーテル基を示す。］ [In Formula (12),
Z ′ represents a direct bond, a sulfonyl group, an alkylene group, a carbonyl group or an ether bond,
A ′ and B ′ each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group. ]
　式（１２）のＺ’、Ａ’及びＢ’は、式（６）のＺ、Ａ及びＢとそれぞれ同義であり、好ましい範囲及び有していてもよい置換基もそれぞれ同義である。 Z ′, A ′, and B ′ in the formula (12) have the same meanings as Z, A, and B in the formula (6), respectively, and the preferred ranges and the substituents that may be included are also the same.
　ポリイミドに含まれる部分構造は、固体ＮＭＲ、ＩＲ等によって原料モノマーの組成を解析することにより求めることができる。
　また、アルカリで溶解した後に、ガスクロマトグラフィー（ＧＣ）、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、二次元ＮＭＲ及び質量分析等によって求めることができる。 The partial structure contained in the polyimide can be obtained by analyzing the composition of the raw material monomer by solid-state NMR, IR, or the like.
Further, after dissolution with alkali, it can be determined by gas chromatography (GC), 1 H-NMR, 13 C-NMR, two-dimensional NMR, mass spectrometry, and the like.
　本発明のポリイミドの形状は特に限定されないが、例えば、粉末状、ペレット状、フィルム状等様々な形態をとることができる。 The shape of the polyimide of the present invention is not particularly limited, but can take various forms such as powder, pellets, and films.
　本発明のポリイミドは、溶媒に可溶であることが好ましい。溶媒に可溶とは、前記で定義した通りであり、用いる溶媒も同義である。溶媒に可溶であることで、キャストやコート等の加工が可能となり、その際に、イミド化反応を伴わないため、温和な条件で加工をすることができる。また、溶液の保存安定性を向上させることができる。 The polyimide of the present invention is preferably soluble in a solvent. Soluble in a solvent is as defined above, and the solvent used is also synonymous. By being soluble in the solvent, processing such as casting and coating becomes possible, and at that time, since imidization reaction is not involved, processing can be performed under mild conditions. Moreover, the storage stability of the solution can be improved.
（ポリイミドの性質）
　本発明のポリイミドの性状及び性質は本発明の主旨を逸脱しない限り特に制限されない。 (Polyimide properties)
The properties and properties of the polyimide of the present invention are not particularly limited without departing from the gist of the present invention.
　本発明のポリイミドの引っ張り強度は、特に制限はないが、通常５０ＭＰａ以上、好ましくは７０ＭＰａ以上であり、通常４００ＭＰａ以下であり、好ましくは３００ＭＰａ以下である。
　引っ張り弾性率は、特に制限はないが、通常１０００ＭＰａ以上、好ましくは１５００ＭＰａ以上であり、通常２０ＧＰａ以下、好ましくは１０ＧＰａ以下である。
　引っ張り伸度は、特段の制限はないが、通常５％ＧＬ以上、好ましくは１０％ＧＬ以上、さらに好ましくは２０ＧＬ％以上であり、通常３００％ＧＬ以下、好ましくは２００ＧＬ％以下である。
　前記したような範囲にあることで、強度があり、特にフィルムとする場合に有用である。これら引っ張り強度、引っ張り弾性率及び引っ張り伸度は、例えば、フィルム状のポリイミドを引っ張り試験機で測定することで求めることができる。 The tensile strength of the polyimide of the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, usually 400 MPa or less, preferably 300 MPa or less.
The tensile elastic modulus is not particularly limited, but is usually 1000 MPa or more, preferably 1500 MPa or more, and usually 20 GPa or less, preferably 10 GPa or less.
The tensile elongation is not particularly limited, but is usually 5% GL or more, preferably 10% GL or more, more preferably 20 GL% or more, and usually 300% GL or less, preferably 200 GL% or less.
By being in the range as described above, there is strength, which is particularly useful when a film is used. These tensile strength, tensile elastic modulus, and tensile elongation can be determined, for example, by measuring film-like polyimide with a tensile tester.
　本発明のポリイミドのガラス転位温度は、特に制限はないが、通常１００℃以上、好ましくは１５０℃以上、より好ましくは２００℃以上である。ガラス転位温度がこの範囲であることで、耐熱性を得ることができる。ガラス転位温度は、例えば、示差走査熱量測定、粘弾性測定、熱重量・示差熱同時分析等を用いることで測定することができる。 The glass transition temperature of the polyimide of the present invention is not particularly limited, but is usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher. When the glass transition temperature is within this range, heat resistance can be obtained. The glass transition temperature can be measured by using, for example, differential scanning calorimetry, viscoelasticity measurement, thermogravimetric / differential thermal simultaneous analysis, and the like.
　本発明のポリイミドの線膨張係数は、１００℃から１５０℃の範囲において、通常６０ｐｐｍ／Ｋ以下、好ましくは５０ｐｐｍ／Ｋ以下、より好ましくは４５ｐｐｍ／Ｋ以下、さらに好ましくは４０ｐｐｍ／Ｋ、特に好ましくは３０ｐｐｍ／Ｋ以下である。この範囲であることで、例えば、ポリイミドをフィルムとして用いたデバイスを作製する際に、寸法安定性が高く、電子素子やカラーフィルター等の部材の破断、変形等を起こしにくくなるため好ましい。測定方法は特に限定されないが、例えば、フィルム状のポリイミドを用いて、実施例の方法にて測定することができる。 The linear expansion coefficient of the polyimide of the present invention is usually 60 ppm / K or less, preferably 50 ppm / K or less, more preferably 45 ppm / K or less, still more preferably 40 ppm / K, particularly preferably in the range of 100 ° C. to 150 ° C. 30 ppm / K or less. This range is preferable because, for example, when a device using polyimide as a film is produced, the dimensional stability is high, and it is difficult for members such as electronic elements and color filters to break and deform. Although the measuring method is not specifically limited, For example, it can measure by the method of an Example using a film-like polyimide.
　本発明のポリイミドの透過率は、フィルムとし、その膜厚が１～１００μｍの場合において、５００ｎｍの光線に対する透過率が通常５５％以上、好ましくは６０％以上、より好ましくは７０％以上である。この範囲となることでデバイスの発光の効率を有効に使用することができる。透過率は、ＪＩＳ　Ｋ　７３６１－１（１９９７年）に記載の方法で測定することができる。 The transmittance of the polyimide of the present invention is a film, and when the film thickness is 1 to 100 μm, the transmittance with respect to a light beam of 500 nm is usually 55% or more, preferably 60% or more, more preferably 70% or more. By being in this range, the light emission efficiency of the device can be used effectively. The transmittance can be measured by the method described in JIS K 7361-1 (1997).
　本発明のポリイミドをフィルムとした際のリタデーションは、使用する波長、例えばデバイス用途であれば４００～８００ｎｍの間の任意の波長で、フィルムの厚さ方向のリタデーション（Ｒｔｈ）は、通常３００ｎｍ以下、好ましくは２００ｎｍ以下、より好ましくは１７０ｎｍ以下、さらに好ましくは１５０ｎｍ以下、よりさらに好ましくは１４０ｎｍ以下、特に好ましくは１２０ｎｍ以下である。フィルムの面内方向のリタデーション（Ｒ０）は、通常１０ｎｍ以下、好ましくは５ｎｍ以下、より好ましくは３ｎｍ以下、さらに好ましくは１ｎｍ以下である。この範囲となることでデバイスの視野性が上がるため好ましい。 When the polyimide of the present invention is used as a film, the retardation is a wavelength to be used, for example, an arbitrary wavelength between 400 and 800 nm for device use, and the retardation in the thickness direction of the film (Rth) is usually 300 nm or less, Preferably it is 200 nm or less, More preferably, it is 170 nm or less, More preferably, it is 150 nm or less, More preferably, it is 140 nm or less, Most preferably, it is 120 nm or less. The in-plane retardation (R0) of the film is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and even more preferably 1 nm or less. This range is preferable because the visibility of the device is improved.
　本発明のポリイミドは、フィルム用途に有用である。また、フィルム用途だけでなく、幅広い用途への応用が可能である。例えば、フレキシブル太陽電池用部材、ディスプレイ用部材、液晶ディスプレイキャリア、耐熱絶縁テープ、耐熱粘着テープ又はコンデンサー若しくはフレキシブルプリント基板用のフィルム等の製造に用いることができる。また、例えば、ガラス繊維や炭素繊維等で補強した構造部材、小型コイルのボビン又は端末絶縁用チューブの成形品の製造等にも用いられる。 The polyimide of the present invention is useful for film applications. In addition to film applications, it can be applied to a wide range of applications. For example, it can be used for production of a flexible solar cell member, a display member, a liquid crystal display carrier, a heat-resistant insulating tape, a heat-resistant adhesive tape, a capacitor or a film for a flexible printed circuit board. Further, for example, it can be used for manufacturing a structural member reinforced with glass fiber or carbon fiber, a small coil bobbin, or a molded product of a terminal insulating tube.
　また、絶縁スペーサー、磁気ヘッドスペーサー又はトランスのスペーサー等の積層材の製造に用いることができる。また、電線・ケーブル絶縁被覆材、低温貯蔵タンク、宇宙断熱材又は集積回路等のエナメルコーティング材の製造に用いることができる。さらに耐熱性を有する糸、織物又は不織布等の製造にも用いることができる。 Also, it can be used for manufacturing laminated materials such as insulating spacers, magnetic head spacers or transformer spacers. Moreover, it can be used for manufacture of enamel coating materials such as electric wire / cable insulation coating materials, low-temperature storage tanks, space insulation materials, and integrated circuits. Furthermore, it can also be used for the production of heat-resistant yarns, woven fabrics or nonwoven fabrics.
（ポリイミドフィルム）
　本発明にかかるポリイミドを用いたポリイミドフィルムの他に、以下の特徴を有するポリイミドフィルムも好ましく用いられる。
　すなわち、本発明はテトラカルボン酸残基及びジアミン残基を含むポリイミドフィルムであって、前記テトラカルボン酸残基及びジアミン残基の少なくともいずれか一方が屈曲部位を有し、線膨張係数が６０ｐｐｍ／Ｋ以下であり、かつ、リタデーションが２００ｎｍ以下であることを特徴とするポリイミドフィルムにも関する。
　テトラカルボン酸残基及びジアミン残基の少なくともいずれか一方が有する屈曲部位の定義は先述した屈曲部位と同様であり、好ましい構造も同様である。 (Polyimide film)
In addition to the polyimide film using the polyimide according to the present invention, a polyimide film having the following characteristics is also preferably used.
That is, the present invention is a polyimide film containing a tetracarboxylic acid residue and a diamine residue, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bent portion, and the linear expansion coefficient is 60 ppm / It is related also to the polyimide film characterized by being below K and retardation being below 200 nm.
The definition of the bending part which at least any one of a tetracarboxylic acid residue and a diamine residue has is the same as that of the bending part mentioned above, and its preferable structure is also the same.
　ポリイミドフィルムの線膨張係数は６０ｐｐｍ／Ｋ以下であればよく、好ましくは５０ｐｐｍ／Ｋ以下、より好ましくは４５ｐｐｍ／Ｋ以下、さらに好ましくは４０ｐｐｍ／Ｋ、特に好ましくは３０ｐｐｍ／Ｋ以下である。また、下限は無く低い方が好ましい。この範囲であることで、例えば、ポリイミドをフィルムとして用いたデバイスを作製する際に、寸法安定性が高く、電子素子やカラーフィルター等の部材の破断、変形等を起こしにくくなるため好ましい。測定方法は特に限定されないが、例えば、フィルム状のポリイミドを用いて、実施例の方法にて測定することができる。 The linear expansion coefficient of the polyimide film may be 60 ppm / K or less, preferably 50 ppm / K or less, more preferably 45 ppm / K or less, still more preferably 40 ppm / K, and particularly preferably 30 ppm / K or less. Moreover, there is no lower limit and the lower one is preferable. This range is preferable because, for example, when a device using polyimide as a film is produced, the dimensional stability is high, and it is difficult for members such as electronic elements and color filters to break and deform. Although the measuring method is not specifically limited, For example, it can measure by the method of an Example using a film-like polyimide.
　ポリイミドフィルムの線膨張係数は６０ｐｐｍ／Ｋ以下とする方法は特に限定されず、例えば、上記ポリイミド前駆体及びポリイミドの少なくともいずれか一方を含む組成物を用いる方法、充填剤等を添加する方法、フィルムを延伸する方法等を行い、これらを適宜調整することで、ポリイミドフィルムの線膨張係数を上記範囲内にすることができる。
　充填剤等は特に限定されないが、例えば、粉末状、粒状、板状、繊維状等の無機系充填剤又は有機系充填剤などが挙げられる。 The method of setting the linear expansion coefficient of the polyimide film to 60 ppm / K or less is not particularly limited. For example, a method using a composition containing at least one of the polyimide precursor and polyimide, a method of adding a filler, and the like, film The linear expansion coefficient of a polyimide film can be made in the said range by performing the method of extending | stretching etc. and adjusting these suitably.
The filler and the like are not particularly limited, and examples thereof include inorganic fillers such as powder, granule, plate, and fiber, or organic fillers.

　無機系充填剤としては、例えば、シリカ、ケイ藻土、バリウムフェライト、酸化ベリリウム、軽石、軽石バルーン等の酸化物；水酸化アルミニウム、水酸化マグネシウム、塩基性炭酸マグネシウム等の水酸化物；炭酸カルシウム、炭酸マグネシウム、ドロマイト、ドーソナイト等の炭酸塩；硫酸カルシウム、硫酸バリウム、硫酸アンモニウム、亜硫酸カルシウム等の硫酸塩及び亜硫酸塩；タルク、クレー、マイカ、アスベスト、ガラス繊維、ガラスバルーン、ガラスビーズ、ケイ酸カルシウム、モンモリロナイト、ベントナイト等のケイ酸塩；炭素繊維、カーボンブラック、グラファイト、炭素中空球等の炭素類；硫化モリブデン、ホウ酸亜鉛、メタホウ酸バリウム、ホウ酸カルシウム、ホウ酸ナトリウム、ボロン繊維等の粉末状、粒状、板状、繊維状の無機質充填剤；金属元素、金属化合物、合金等の粉末状、粒状、繊維状、ウイスカー状の金属充填剤；炭化ケイ素、窒化ケイ素、ジルコニア、窒化アルミニウム、炭化チタン、チタン酸カリウム等の粉末状、粒状、繊維状、ウイスカー状のセラミックス充填剤；等が挙げられる。
Examples of inorganic fillers include oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice and pumice balloon; hydroxides such as aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate; calcium carbonate Carbonates such as magnesium carbonate, dolomite, and dawsonite; sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, and calcium sulfite; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate Silicates such as carbon fiber, carbon black, graphite and carbon hollow spheres; powders of molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate, boron fiber, etc. Shape, granular, board , Fibrous inorganic fillers; powdered, granular, fibrous, whisker-like metal fillers of metal elements, metal compounds, alloys, etc .; silicon carbide, silicon nitride, zirconia, aluminum nitride, titanium carbide, potassium titanate, etc. Powdered, granular, fibrous, and whisker-like ceramic fillers.
　一方、有機系充填剤としては、例えば、カーボンナノチューブ、フラーレン、芳香族ポリアミド繊維、セルロース繊維、ナイロン繊維、ポリエステル繊維、ポリプロピレン繊維、熱硬化性樹脂粉末、ゴム等を挙げることができる。
　充填剤としては、不織布等平板状に加工したものを用いてもよいし、複数の材料を混ぜて用いてもよい。
　線膨張係数は熱機械的装置により測定することができる。 On the other hand, examples of the organic filler include carbon nanotubes, fullerenes, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, polypropylene fibers, thermosetting resin powders, and rubbers.
As a filler, what processed into flat form, such as a nonwoven fabric, may be used, and several materials may be mixed and used.
The linear expansion coefficient can be measured by a thermomechanical device.
　ポリイミドフィルムのリタデーションは２００ｎｍ以下であればよく、好ましくは１７０ｎｍ以下、より好ましくは１５０ｎｍ以下、更に好ましくは１４０ｎｍ以下、特に好ましくは１２０ｎｍ以下である。フィルムの面内方向のリタデーション（Ｒ０）は、通常１０ｎｍ以下、好ましくは５ｎｍ以下、より好ましくは３ｎｍ以下、さらに好ましくは１ｎｍ以下である。この範囲となることでデバイスの視野性が上がるため好ましい。
　ポリイミドフィルムのリタデーションを２００ｎｍ以下とする方法は特に限定されず、例えば、上記ポリイミド前駆体及びポリイミドの少なくともいずれか一方を含む組成物を用いる方法、負のリタデーションを有する化合物又は樹脂を混合する方法、ポリイミドと同等の線膨張係数を有する基材を用いて製膜する方法等を用いることで、ポリイミドフィルムのリタデーションを上記範囲内にすることができる。
　負のリタデーションを有する化合物又は樹脂は特に限定されないが、例えば、スチレン系化合物、アクリル系化合物、スチレン系樹脂、アクリル樹脂等が挙げられる。
　ポリイミドと同等の線膨張係数を有する基材としては、金属箔、樹脂基板等が挙げられる。
　リタデーションは位相差フィルム・光学材料検査装置などにより測定することができる。 The retardation of the polyimide film may be 200 nm or less, preferably 170 nm or less, more preferably 150 nm or less, still more preferably 140 nm or less, and particularly preferably 120 nm or less. The in-plane retardation (R0) of the film is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and even more preferably 1 nm or less. This range is preferable because the visibility of the device is improved.
The method of setting the retardation of the polyimide film to 200 nm or less is not particularly limited. For example, a method using a composition containing at least one of the polyimide precursor and polyimide, a method of mixing a compound having a negative retardation, or a resin, The retardation of a polyimide film can be made into the said range by using the method etc. which form into a film using the base material which has a linear expansion coefficient equivalent to a polyimide.
The compound or resin having negative retardation is not particularly limited, and examples thereof include a styrene compound, an acrylic compound, a styrene resin, and an acrylic resin.
Examples of the base material having a linear expansion coefficient equivalent to that of polyimide include a metal foil and a resin substrate.
Retardation can be measured by a retardation film / optical material inspection apparatus or the like.
　本発明のポリイミドフィルムの透過率は、その膜厚が１～１００μｍの場合において、５００ｎｍの光線に対する透過率が通常５５％以上、好ましくは６０％以上、より好ましくは７０％以上である。この範囲となることでデバイスの発光の効率を有効に使用することができる。透過率は、ＪＩＳ　Ｋ　７３６１－１（１９９７年）に記載の方法で測定することができる。 When the film thickness is 1 to 100 μm, the transmittance of the polyimide film of the present invention is usually 55% or more, preferably 60% or more, more preferably 70% or more with respect to a light beam of 500 nm. By being in this range, the light emission efficiency of the device can be used effectively. The transmittance can be measured by the method described in JIS K 7361-1 (1997).
　本発明のポリイミドフィルムにおいて、膜厚１０μｍでの黄色度（イエローインデックス：ＹＩ）は、通常－１０以上、好ましくは－５以上、より好ましくは－１以上である。一方、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。この範囲となることで、ポリイミドをデバイス部材として用いた際に、発光の効率を有効に使用することができる。イエローインデックスは、例えば分光側色計等を用いることで測定することができる。 In the polyimide film of the present invention, the yellowness (yellow index: YI) at a film thickness of 10 μm is usually −10 or more, preferably −5 or more, more preferably −1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less. By being in this range, when polyimide is used as a device member, the efficiency of light emission can be used effectively. The yellow index can be measured by using, for example, a spectral color meter.
　ポリイミドフィルムの厚さは、特に制限はないが、通常１μｍ以上、好ましくは２μｍ以上であり、一方、通常２００μｍ以下、好ましくは１００μｍ以下である。フィルムが適当な厚さであることで、十分な耐性を保持し、且つ、フレキシブルデバイスの薄型化が可能となる。 The thickness of the polyimide film is not particularly limited, but is usually 1 μm or more, preferably 2 μm or more, and is usually 200 μm or less, preferably 100 μm or less. When the film has an appropriate thickness, sufficient resistance can be maintained and the flexible device can be thinned.
（ポリイミドフィルムの製造方法）
　本発明のポリイミドフィルムの製造方法は特に制限はないが、例えば、前記方法によって得られたポリイミド前駆体及び／又はポリイミドを含む組成物をキャリア基板上に塗布した後、溶媒を揮発させることによって得ることができる。塗布の方法は、均一な厚さの層を形成できる方法であれば特に制限されないが、例えば、ダイコーティング、スピンコーティング、スクリーン印刷、スプレー、アプリケーターを用いたキャスティング法、コーターを用いる方法、吹き付けによる方法、浸漬法、カレンダー法、流延法等が挙げられる。これらの方法は、塗布面積及び被塗布面の形状等に応じて適宜選択することができる。 (Production method of polyimide film)
Although there is no restriction | limiting in particular in the manufacturing method of the polyimide film of this invention, For example, after apply | coating the composition containing the polyimide precursor and / or polyimide which were obtained by the said method on a carrier substrate, it obtains by volatilizing a solvent. be able to. The application method is not particularly limited as long as it can form a layer having a uniform thickness. For example, die coating, spin coating, screen printing, spraying, a casting method using an applicator, a method using a coater, and spraying. Examples thereof include a method, a dipping method, a calendar method, and a casting method. These methods can be appropriately selected according to the application area, the shape of the surface to be applied, and the like.
　被塗布材料の基板としては、例えば、フロートガラス、ソーダガラス等のガラス、ポリエチレンテレフタレート、ポリカーボネート、ポリオレフィン等のプラスチックからなる基板を用いることができる。このような基板に塗布する際には、基板の表面に、官能性シラン含有化合物、官能性チタン含有化合物をあらかじめと伏せうることもできる。また、紫外線処理、プラズマ処理等を行うこともできる。 As the substrate of the material to be coated, for example, a substrate made of glass such as float glass or soda glass, or a plastic such as polyethylene terephthalate, polycarbonate, or polyolefin can be used. When applying to such a substrate, a functional silane-containing compound or a functional titanium-containing compound can be prefaced on the surface of the substrate. Further, ultraviolet treatment, plasma treatment, or the like can be performed.
　ポリイミド前駆体及び／又はポリイミド組成物の溶媒を揮発させる方法も特に制限されない。通常は、溶媒を減圧下で揮発させる方法及び／又は、塗布された被塗布材料を加熱することにより、溶媒が揮発させられる。加熱方法は特に限定されず、熱風加熱、真空加熱、赤外線加熱、マイクロ波加熱、熱板もしくはホットロール等を用いた接触による加熱等が挙げられる。 The method for volatilizing the solvent of the polyimide precursor and / or the polyimide composition is not particularly limited. Usually, the solvent is volatilized by heating the applied material to be coated and / or by volatilizing the solvent under reduced pressure. The heating method is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, heating by contact using a hot plate or a hot roll, and the like.
　溶媒を揮発させるときの加熱温度は、溶媒の種類に応じて好適な温度を用いることができるが、通常２０℃以上、好ましくは４０℃以上、より好ましくは５０℃以上、さらに好ましくは６０℃以上である。また通常４００℃以下、好ましくは３８０℃以下、より好ましくは３５０℃以下、さらに好ましくは３００℃以下である。温度が上記下限以上であることで、残留溶媒を低減することができ、十分に乾燥することができる。また、上記上限以下であることで、急激な揮発によって発生する気泡等を抑制することができ、外観や品質を良好に保つことができる。
　加熱の雰囲気は、空気下でも不活性雰囲気下でも良く特に制限はないが、ポリイミドフィルムに無色透明性が要求される場合は、着色抑制のために窒素などの不活性雰囲気下で加熱することが好ましい。 The heating temperature for volatilizing the solvent can be a suitable temperature depending on the type of the solvent, but is usually 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher, more preferably 60 ° C. or higher. It is. Moreover, it is 400 degrees C or less normally, Preferably it is 380 degrees C or less, More preferably, it is 350 degrees C or less, More preferably, it is 300 degrees C or less. When the temperature is equal to or higher than the above lower limit, the residual solvent can be reduced and the film can be sufficiently dried. Moreover, by being below the said upper limit, the bubble etc. which generate | occur | produce by rapid volatilization can be suppressed and an external appearance and quality can be kept favorable.
The heating atmosphere may be either air or an inert atmosphere, and is not particularly limited. However, if the polyimide film is required to be colorless and transparent, it can be heated under an inert atmosphere such as nitrogen to suppress coloring. preferable.
　上記塗布、乾燥によってキャリア上に形成されたポリイミドフィルムを剥離する方法は特に制限はないが、例えばレーザー剥離、機械剥離、水やお湯への浸漬による剥離などが挙げられる。 The method for peeling the polyimide film formed on the carrier by coating and drying is not particularly limited, and examples thereof include laser peeling, mechanical peeling, and peeling by immersion in water or hot water.
　ポリイミド前駆体組成物を用いた膜及び／またはポリイミドフィルムを製造する方法として、前記ポリイミド前駆体樹脂及び／又はポリイミド樹脂を溶融し、成形する方法、例えば、射出成型法、押出成形法、中空成形法、圧縮成型法、積層形成法、ロール加工法、延伸加工法、スタンプ加工法、熱プレス法、Ｔ－ダイ法等が挙げられる。 As a method for producing a film and / or a polyimide film using a polyimide precursor composition, a method for melting and molding the polyimide precursor resin and / or polyimide resin, for example, an injection molding method, an extrusion molding method, a hollow molding method. Method, compression molding method, laminate formation method, roll processing method, stretching processing method, stamp processing method, hot press method, T-die method and the like.
　以下、実施例及び比較例を挙げて本発明をさらに詳細に説明する。なお、以下の実施例は本発明を詳細に説明するために示すものであり、本発明はその主旨に反しない限り、以下の実施例に限定されるものではない。なお、以下の実施例における各種の条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としても意味を持つものであり、好ましい範囲は、前記の上限又は下限の値と実施例の値又は実施例同士の値との組み合わせにて規定される範囲であってもよい。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In addition, the following examples are shown in order to describe the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof. In addition, the values of various conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above upper limit or lower limit value. It may be a range defined by a combination of values of the examples or values between the examples.
　[実施例１] 
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）５．７ｇ（０．０１９ｍｏｌ）、３，３’，４，４’－ビシクロヘキサンテトラカルボン酸二無水物（Ｈ－ＢＰＤＡ）２．６ｇ（０．００９ｍｏｌ）、ピロメリット酸無水物（ＰＭＤＡ）１．４ｇ（０．００６ｍｏｌ）、２，２’－ビス（トリフルオロメチル）ベンジジン（６Ｆ－ｍ－ＴＢ）５．６ｇ（０．０１８ｍｏｌ）、４，４’－ジアミノジフェニルスルホン４．３ｇ（０．０１８ｍｏｌ）、Ｎ－メチル－２－ピロリドン（ＮＭＰ）７３ｇを加えた。この混合物を撹拌しながら昇温し、８０℃で６時間反応させ、ポリイミド前駆体を含む組成物１を得た。 [Example 1]
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer, 5.7 g (0.019 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3, 2.6 g (0.009 mol) of 3 ′, 4,4′-bicyclohexanetetracarboxylic dianhydride (H-BPDA), 1.4 g (0.006 mol) of pyromellitic anhydride (PMDA), 2,2 5.6 g (0.018 mol) of '-bis (trifluoromethyl) benzidine (6F-m-TB), 4.3 g (0.018 mol) of 4,4'-diaminodiphenylsulfone, N-methyl-2-pyrrolidone ( NMP) 73 g was added. The mixture was heated while stirring and reacted at 80 ° C. for 6 hours to obtain a composition 1 containing a polyimide precursor.
（ポリイミドフィルムの作製）
　得られた組成物１をガラス基板上に１００μｍのアプリケーターを用いて塗布し、３５０℃で３０分加熱することによって、膜厚１０μｍのポリイミドフィルム１を得た。 (Preparation of polyimide film)
The obtained composition 1 was applied on a glass substrate using a 100 μm applicator and heated at 350 ° C. for 30 minutes to obtain a polyimide film 1 having a thickness of 10 μm.
（線膨張係数（ＣＴＥ）の測定）
　気温２５℃湿度５０％の恒温恒湿室で一晩以上調湿したポリイミドフィルム１を幅４ｍｍ、長さ４０ｍｍのスーパーストレートカッターにより打ち抜き、エスアイアイ・ナノテクノロジー社製ＴＭＡ／ＳＳ６１００を使用して測定した。フィルムサンプルのチャック間距離は１０ｍｍ、窒素１２０ｍＬ／ｍｉｎ、３０℃から２１０℃に昇温速度１０℃／ｍｉｎのときの１００℃と１５０℃の間のＣＴＥを表２に記載した。 (Measurement of linear expansion coefficient (CTE))
A polyimide film 1 conditioned at least overnight in a constant temperature and humidity chamber with a temperature of 25 ° C. and a humidity of 50% is punched with a super straight cutter with a width of 4 mm and a length of 40 mm, and measured using a TMA / SS6100 manufactured by SII Nanotechnology. did. Table 2 shows the CTE between 100 ° C. and 150 ° C. when the distance between chucks of the film sample is 10 mm, nitrogen is 120 mL / min, and the temperature rising rate is 10 ° C./min from 30 ° C. to 210 ° C.
（フィルムの厚さ方向のリタデーション（Ｒｔｈ）値の測定）
　ポリイミドフィルム１のフィルムの厚さ方向のリタデーション（Ｒｔｈ）値を、測定位相差フィルム・光学材料検査装置（大塚電子社製「ＲＥＴＳ１００」）を用いて測定・算出を行った。測定結果を表２に示す。今回用いたフィルムの厚さ方向のリタデーション（Ｒｔｈ）値は、波長４６０ｎｍ、フィルム厚さ１０μｍのときの値である。 (Measurement of retardation (Rth) value in the thickness direction of the film)
The retardation (Rth) value in the thickness direction of the polyimide film 1 was measured and calculated using a measurement retardation film / optical material inspection apparatus ("RETS100" manufactured by Otsuka Electronics Co., Ltd.). The measurement results are shown in Table 2. The retardation (Rth) value in the thickness direction of the film used this time is a value at a wavelength of 460 nm and a film thickness of 10 μm.
（イエローインデックス（ＹＩ）値の測定）
　ポリイミドフィルム１のイエローインデックス（ＹＩ）値を、スガ試験機（株）製ＳＭカラーコンピューターＳＭ５を用いて測定した。今回用いたＹＩ値はフィルム膜厚１０μｍあたりのＹＩ値として算出した値である。 (Measurement of yellow index (YI) value)
The yellow index (YI) value of the polyimide film 1 was measured using SM color computer SM5 manufactured by Suga Test Instruments Co., Ltd. The YI value used this time is a value calculated as a YI value per 10 μm of film thickness.
［実施例２］
　実施例１のＢＰＡＤを１．７ｇ（０．００６ｍｏｌ）、Ｈ－ＢＰＤＡを１．８ｇ（０．００６ｍｏｌ）、ＰＭＤＡを３．９ｇ（０．０１８ｍｏｌ）、６Ｆ－ｍ－ＴＢを５．５ｇ（０．０１７ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを３．２ｇ（０．０１３ｍｏｌ）、ＮＭＰを６５ｇに変更した以外は実施例１と同法の方法でポリイミド前駆体組成物２及びポリイミドフィルム２を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 2]
In Example 1, BPAD was 1.7 g (0.006 mol), H-BPDA was 1.8 g (0.006 mol), PMDA was 3.9 g (0.018 mol), and 6F-m-TB was 5.5 g (0 0.017 mol), polyimide precursor composition 2 and polyimide film 2 were prepared in the same manner as in Example 1 except that 3.2 g (0.013 mol) of 4,4′-diaminodiphenylsulfone and NMP were changed to 65 g. Obtained. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
　［実施例３］
　実施例１のＢＰＤＡを５．３ｇ（０．０１８ｍｏｌ）、Ｈ－ＢＰＤＡを２．５ｇ（０．００８ｍｏｌ）、ＰＭＤＡを１．３ｇ（０．００６ｍｏｌ）、６Ｆ－ｍ－ＴＢを７．９ｇ（０．０２５ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを２．０ｇ（０．００８ｍｏｌ）に、ＮＭＰを７１ｇに変更した以外は実施例１と同様の方法でポリイミド前駆体組成物３及びポリイミドフィルム３を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 3]
5.3 g (0.018 mol) of BPDA of Example 1, 2.5 g (0.008 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 7.9 g of 0F-m-TB (0 0.025 mol), 4,4′-diaminodiphenylsulfone was changed to 2.0 g (0.008 mol), and NMP was changed to 71 g, and polyimide precursor composition 3 and polyimide film 3 were prepared in the same manner as in Example 1. Obtained. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例４］
　実施例１のＢＰＤＡを５．４ｇ（０．０１８ｍｏｌ）、Ｈ－ＢＰＤＡを２．５ｇ（０．００８ｍｏｌ）、ＰＭＤＡを１．３ｇ（０．００６ｍｏｌ）、６Ｆ－ｍ－ＴＢを９．５ｇ（０．０３ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを０．８ｇ（０．００３ｍｏｌ）、ＮＭＰを７８ｇに変更した以外は実施例１と同様の方法でポリイミド前駆体組成物４及びポリイミドフィルム４を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 4]
5.4 g (0.018 mol) of BPDA of Example 1, 2.5 g (0.008 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 9.5 g of 6F-m-TB (0 0.03 mol), 4,4′-diaminodiphenyl sulfone was changed to 0.8 g (0.003 mol), and NMP was changed to 78 g to obtain a polyimide precursor composition 4 and a polyimide film 4 in the same manner as in Example 1. It was. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例５］
　還流窒素ガス導入管、冷却器、トルエンを満たしたディーンスターク凝集器、及び攪拌機を備えた４つ口フラスコに、ＢＰＤＡ４．９ｇ（０．０１７ｍｏｌ）、Ｈ－ＢＰＤＡ２．３ｇ（０．００７ｍｏｌ）、ＰＭＤＡ１．２ｇ（０．００６ｍｏｌ）、６Ｆ－ｍ－ＴＢ８．６ｇ（０．０２７ｍｏｌ）、４，４’－ジアミノジフェニルスルホン０．７ｇ（０．００３ｍｏｌ）、ＮＭＰ７１ｇ、トルエン１４ｇを加えた。この混合物を撹拌しながら２００℃で１３時間加熱還流し、ポリイミド組成物５を得た。 [Example 5]
A four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer was charged with 4.9 g (0.017 mol) of BPDA, 2.3 g (0.007 mol) of H-BPDA, and PMDA1. 0.2 g (0.006 mol), 6F-m-TB 8.6 g (0.027 mol), 4,4′-diaminodiphenylsulfone 0.7 g (0.003 mol), NMP 71 g, and toluene 14 g were added. The mixture was heated to reflux at 200 ° C. for 13 hours with stirring to obtain a polyimide composition 5.
［実施例６］
　実施例１のＢＰＤＡを４．１ｇ（０．０１４ｍｏｌ）、Ｈ－ＢＰＤＡを２．１ｇ（０．００７ｍｏｌ）、ＰＭＤＡを１．９ｇ（０．００９ｍｏｌ）、６Ｆ－ｍ－ＴＢを８．４ｇ（０．０２６ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを２．２ｇ（０．００９ｍｏｌ）、ＮＭＰを８２ｇに変更し、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物１．９ｇ（０．００５ｍｏｌ）を追加した以外は実施例１と同様の方法でポリイミド前駆体組成物６及びポリイミドフィルム６を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 6]
4.1 g (0.014 mol) of BPDA of Example 1, 2.1 g (0.007 mol) of H-BPDA, 1.9 g (0.009 mol) of PMDA, and 8.4 g of 0F-m-TB (0 .026 mol), 2.2 g (0.009 mol) of 4,4′-diaminodiphenylsulfone and NMP of 82 g were changed to 1.9 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride. A polyimide precursor composition 6 and a polyimide film 6 were obtained in the same manner as in Example 1 except that (0.005 mol) was added. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例７］
　実施例６のＢＰＤＡを５．４ｇ（０．０１８ｍｏｌ）、Ｈ－ＢＰＤＡを１．２ｇ（０．００４ｍｏｌ）、ＰＭＤＡを１．３ｇ（０．００６ｍｏｌ）、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物を１．５ｇ（０．００４ｍｏｌ）、６Ｆ－ｍ－ＴＢを７．９ｇ（０．０２５ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを２．０ｇ（０．００８ｍｏｌ）、ＮＭＰを７８ｇに変更した以外は実施例６と同様の方法でポリイミド前駆体組成物７及びポリイミドフィルム７を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 7]
5.4 g (0.018 mol) of BPDA of Example 6, 1.2 g (0.004 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 3,3 ′, 4,4′-diphenyl 1.5 g (0.004 mol) of sulfonetetracarboxylic dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 2.0 g (0.008 mol) of 4,4′-diaminodiphenylsulfone, A polyimide precursor composition 7 and a polyimide film 7 were obtained in the same manner as in Example 6 except that NMP was changed to 78 g. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例８］
　実施例６のＢＰＤＡを５．４ｇ（０．０１８ｍｏｌ）、Ｈ－ＢＰＤＡを２．０ｇ（０．００７ｍｏｌ）、ＰＭＤＡを１．３ｇ（０．００６ｍｏｌ）、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物を０．６ｇ（０．００２ｍｏｌ）、６Ｆ－ｍ－ＴＢを７．９ｇ（０．０２５ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを２．０ｇ（０．００８ｍｏｌ）、ＮＭＰを７７ｇに変更した以外は実施例６と同様の方法でポリイミド前駆体組成物８及びポリイミドフィルム８を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 8]
5.4 g (0.018 mol) of BPDA of Example 6, 2.0 g (0.007 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 3,3 ′, 4,4′-diphenyl 0.6 g (0.002 mol) of sulfonetetracarboxylic dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 2.0 g (0.008 mol) of 4,4′-diaminodiphenylsulfone, A polyimide precursor composition 8 and a polyimide film 8 were obtained in the same manner as in Example 6 except that NMP was changed to 77 g. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例９］
　実施例６のＢＰＤＡを５．９ｇ（０．０１９ｍｏｌ）、Ｈ－ＢＰＤＡを１．９ｇ（０．００６ｍｏｌ）、ＰＭＤＡを１．４ｇ（０．００６ｍｏｌ）、６Ｆ－ｍ－ＴＢを７．７ｇ（０．０２４ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを１．２ｇ（０．００５ｍｏｌ）、ＮＭＰを７６ｇに変更し、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物を９，９－ビス（４－アミノフェニル）フルオレン１．１ｇ（０．００３ｍｏｌ）に変更した以外は実施例６と同様の方法でポリイミド前駆体組成物９及びポリイミドフィルム９を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 9]
In Example 6, 5.9 g (0.019 mol) of BPDA, 1.9 g (0.006 mol) of H-BPDA, 1.4 g (0.006 mol) of PMDA, 7.7 g of 0F-m-TB (0 .024 mol), 4,4′-diaminodiphenylsulfone 1.2 g (0.005 mol), NMP 76 g, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 9, A polyimide precursor composition 9 and a polyimide film 9 were obtained in the same manner as in Example 6 except that the amount was changed to 1.1 g (0.003 mol) of 9-bis (4-aminophenyl) fluorene. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例１０］
　実施例６のＢＰＤＡを９．８ｇ（０．０３３ｍｏｌ）、Ｈ－ＢＰＤＡを２．３ｇ（０．００７ｍｏｌ）、ＰＭＤＡを２．４ｇ（０．０１１ｍｏｌ）、６Ｆ－ｍ－ＴＢを１８．０ｇ（０．０５６ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを４．７ｇ（０．０１９ｍｏｌ）、ＮＭＰを１４１ｇに変更し、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物を２，２－ビス（３，４－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物９．９ｇ（０．０２２ｍｏｌ）に変更した以外は実施例６と同様の方法でポリイミド前駆体組成物１０及びポリイミドフィルム１０を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 10]
9.8 g (0.033 mol) of BPDA of Example 6, 2.3 g (0.007 mol) of H-BPDA, 2.4 g (0.011 mol) of PMDA, and 18.0 g (0 of 0) of F-m-TB 0.056 mol), 4.7 g (0.019 mol) of 4,4′-diaminodiphenylsulfone, and 141 g of NMP, and 2,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride was changed to 2, The same as Example 6 except that the amount was changed to 9.9 g (0.022 mol) of 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride. The polyimide precursor composition 10 and the polyimide film 10 were obtained by the method. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例１１］
　実施例１０のＢＰＤＡを３．８ｇ（０．０１３ｍｏｌ）、Ｈ－ＢＰＤＡを２．０ｇ（０．００７ｍｏｌ）、ＰＭＤＡを１．７ｇ（０．００８ｍｏｌ）、２，２－ビス（３，４－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物を２．１ｇ（０．００５ｍｏｌ）、６Ｆ－ｍ－ＴＢを７．９ｇ（０．０２５ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを２．０ｇ（０．００８ｍｏｌ）、ＮＭＰを７９ｇに変更した以外は実施例１０と同様の方法でポリイミド前駆体組成物１１及びポリイミドフィルム１１を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 11]
3.8 g (0.013 mol) of BPDA of Example 10, 2.0 g (0.007 mol) of H-BPDA, 1.7 g (0.008 mol) of PMDA, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2.1 g (0.005 mol), 6F-m-TB 7.9 g (0.025 mol), 4,4 A polyimide precursor composition 11 and a polyimide film 11 were obtained in the same manner as in Example 10, except that 2.0 g (0.008 mol) of '-diaminodiphenylsulfone and 79 g of NMP were changed. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例１２］
　実施例１０のＢＰＤＡを６．６ｇ（０．０２２ｍｏｌ）、Ｈ－ＢＰＤＡを２．２ｇ（０．００７ｍｏｌ）、ＰＭＤＡを４．９ｇ（０．０２２ｍｏｌ）、ＮＭＰを１３９ｇに変更した以外は実施例１０と同様の方法でポリイミド前駆体組成物１２及びポリイミドフィルム１２を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 12]
Example 10 except that BPDA of Example 10 was changed to 6.6 g (0.022 mol), H-BPDA was changed to 2.2 g (0.007 mol), PMDA was changed to 4.9 g (0.022 mol), and NMP was changed to 139 g. The polyimide precursor composition 12 and the polyimide film 12 were obtained by the same method. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例１３］
　実施例９のＢＰＤＡを５．２ｇ（０．０１８ｍｏｌ）、Ｈ－ＢＰＤＡを１．８ｇ（０．００６ｍｏｌ）、ＰＭＤＡを１．３ｇ（０．００６ｍｏｌ）、６Ｆ－ｍ－ＴＢを６．２ｇ（０．０２０ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを１．９ｇ（０．００８ｍｏｌ）、ＮＭＰを５３ｇに変更し、９，９－ビス（４－アミノフェニル）フルオレンを２，２－ビス（３－アミノ－４－ヒドロキシフェニル）－ヘキサフルオロプロパン１．１ｇ（０．００３ｍｏｌ）に変更した以外は実施例９と同様の方法でポリイミド前駆体組成物１３及びポリイミドフィルム１３を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ、及びＹＩの測定を行った。結果を表２に示す。 [Example 13]
5.2 g (0.018 mol) of BPDA of Example 9, 1.8 g (0.006 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 6.2 g of 6F-m-TB (0 .020 mol), 1.9 g (0.008 mol) of 4,4′-diaminodiphenylsulfone, 53 g of NMP, and 9,9-bis (4-aminophenyl) fluorene with 2,2-bis (3- A polyimide precursor composition 13 and a polyimide film 13 were obtained in the same manner as in Example 9 except that 1.1 g (0.003 mol) of amino-4-hydroxyphenyl) -hexafluoropropane was used. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例１４］
　実施例１のＢＰＡＤを６．６ｇ（０．０２２ｍｏｌ）、Ｈ－ＢＰＤＡを３．０ｇ（０．０１０ｍｏｌ）、ＰＭＤＡを１．６ｇ（０．００７ｍｏｌ）、６Ｆ－ｍ－ＴＢを９．６ｇ（０．０３０ｍｏｌ）、ＮＭＰを７３ｇに変更し、４，４’－ジアミノジフェニルスルホンを１，４－ビス［２－（４－アミノフェニル）－２－プロピル］ベンゼン３．４ｇ（０．０１０ｍｏｌ）に変更した以外は実施例１と同法の方法でポリイミド前駆体組成物１４及びポリイミドフィルム１４を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 14]
The BPAD of Example 1 was 6.6 g (0.022 mol), H-BPDA was 3.0 g (0.010 mol), PMDA was 1.6 g (0.007 mol), and 6F-m-TB was 9.6 g (0 .030 mol), NMP was changed to 73 g, and 4,4′-diaminodiphenyl sulfone was changed to 3.4 g (0.010 mol) of 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene. A polyimide precursor composition 14 and a polyimide film 14 were obtained by the same method as in Example 1 except that. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［実施例１５］
　実施例１４の１，４－ビス［２－（４－アミノフェニル）－２－プロピル］ベンゼンを１，３－ビス［２－（４－アミノフェニル）－２－プロピル］ベンゼンに変更した以外は実施例１３と同法の方法でポリイミド前駆体組成物１４及びポリイミドフィルム１４を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Example 15]
Except that 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene of Example 14 was changed to 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene A polyimide precursor composition 14 and a polyimide film 14 were obtained by the same method as in Example 13. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例１］
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、ＢＰＤＡ４．４ｇ（０．０１５ｍｏｌ）、Ｈ－ＢＰＤＡ２．３ｇ（０．００８ｍｏｌ）、ＰＭＤＡ３．３ｇ（０．０１５ｍｏｌ）、６Ｆ－ｍ－ＴＢ１２．２ｇ（０．０３８ｍｏｌ）、ＮＭＰ７６ｇを加えた。この混合物を撹拌しながら昇温し、８０℃で６時間反応させ、ポリイミド前駆体を含む組成物１６を得た。得られた組成物１６から実施例１と同様にして、ポリイミドフィルム１６を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 1]
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser and a stirrer, 4.4 g (0.015 mol) of BPDA, 2.3 g (0.008 mol) of H-BPDA, 3.3 g (0.015 mol) of PMDA, 6F— 12.2 g (0.038 mol) of m-TB and 76 g of NMP were added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 16 containing a polyimide precursor. A polyimide film 16 was obtained from the obtained composition 16 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例２］
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、Ｈ－ＢＰＤＡ１．８ｇ（０．００６ｍｏｌ）、ＰＭＤＡ５．２ｇ（０．０２４ｍｏｌ）、６Ｆ－ｍ－ＴＢ７．２ｇ（０．０２３ｍｏｌ）、４，４’－ジアミノジフェニルスルホン１．９ｇ（０．００８ｍｏｌ）、ＮＭＰ６４ｇを加えた。この混合物を撹拌しながら昇温し、８０℃で６時間反応させ、ポリイミド前駆体を含む組成物１７を得た。得られた組成物１７から実施例１と同様にポリイミドフィルム１７を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 2]
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer, H-BPDA 1.8 g (0.006 mol), PMDA 5.2 g (0.024 mol), 6F-m-TB 7.2 g (0.023 mol) ), 4,4′-diaminodiphenylsulfone (1.9 g, 0.008 mol) and NMP (64 g) were added. The mixture was heated while stirring and reacted at 80 ° C. for 6 hours to obtain a composition 17 containing a polyimide precursor. A polyimide film 17 was obtained from the obtained composition 17 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例３］
　還流窒素ガス導入管、冷却器、アニソールを満たしたディーンスターク凝集器及び攪拌機を備えた４つ口フラスコに、ＢＰＤＡ１４．６ｇ（０．０５０ｍｏｌ）、Ｈ－ＢＰＤＡ１５．２ｇ（０．０５０ｍｏｌ）、６Ｆ－ｍ－ＴＢ１６．０ｇ（０．０５ｍｏｌ）、４，４’－ジアミノジフェニルスルホン９．９ｇ（０．０４ｍｏｌ）、３，３’－ジアミノジフェニルスルホン２．５ｇ（０．０１ｍｏｌ）、ＮＭＰ８７ｇ、アニソール８７ｇを加えた。この混合物を撹拌しながら２００℃で１３時間加熱還流し、ポリイミド組成物１８を得た。得られた組成物１８から実施例１と同様にポリイミドフィルム１８を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 3]
In a four-necked flask equipped with a refluxing nitrogen gas introduction tube, a condenser, a Dean-Stark agglomerator filled with anisole, and a stirrer, 14.6 g (0.050 mol) of BPDA, 15.2 g (0.050 mol) of H-BPDA, 6F— m-TB 16.0 g (0.05 mol), 4,4′-diaminodiphenyl sulfone 9.9 g (0.04 mol), 3,3′-diaminodiphenyl sulfone 2.5 g (0.01 mol), NMP 87 g, anisole 87 g added. The mixture was heated to reflux at 200 ° C. for 13 hours with stirring to obtain a polyimide composition 18. A polyimide film 18 was obtained from the obtained composition 18 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例４］
　実施例１のＢＰＡＤを５．６ｇ（０．０１９ｍｏｌ）、ＰＭＤＡを１．４ｇ（０．００６ｍｏｌ）、６Ｆ－ｍ－ＴＢを７．７ｇ（０．０２４ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを２．０ｇ（０．００８ｍｏｌ）、ＮＭＰを７６ｇに変更し、Ｈ－ＢＰＤＡを３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物２．３ｇ（０．００６ｍｏｌ）に変更した以外は実施例１と同法の方法でポリイミド前駆体組成物１９及びポリイミドフィルム１９得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 4]
5.6 g (0.019 mol) of BPAD of Example 1, 1.4 g (0.006 mol) of PMDA, 7.7 g (0.024 mol) of 6F-m-TB, and 4,4′-diaminodiphenylsulfone Other than changing 2.0 g (0.008 mol), NMP to 76 g, and changing H-BPDA to 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 2.3 g (0.006 mol) Obtained a polyimide precursor composition 19 and a polyimide film 19 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例５］
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、ＢＰＤＡ３．６ｇ（０．０１２ｍｏｌ）、Ｈ－ＢＰＤＡ３．８ｇ（０．０１２ｍｏｌ）、２、２’－ジメチルベンジジン（ｍ－ＴＢ）５．３ｇ（０．０２５ｍｏｌ）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）３８ｇを加えた。この混合物を撹拌しながら昇温し８０℃で６時間反応させ、ポリイミド前駆体を含む組成物２１を得た。得られた組成物２１から実施例１と同様にポリイミドフィルム２１を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 5]
To a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer, 3.6 g (0.012 mol) of BPDA, 3.8 g (0.012 mol) of H-BPDA, 2,2′-dimethylbenzidine (m-TB) ) 5.3 g (0.025 mol) and 38 g of N, N-dimethylacetamide (DMAc) were added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 21 containing a polyimide precursor. A polyimide film 21 was obtained from the resulting composition 21 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例６］
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、ＢＰＤＡ５．８ｇ（０．０２ｍｏｌ）、６Ｆ－ｍ－ＴＢ６．４ｇ（０．０２０ｍｏｌ）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）３７ｇを加えた。この混合物を撹拌しながら昇温し８０℃で６時間反応させ、ポリイミド前駆体を含む組成物２２を得た。得られた組成物２２から実施例１と同様にポリイミドフィルム２２を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 6]
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer, 5.8 g (0.02 mol) of BPDA, 6.4 g (0.020 mol) of 6F-m-TB, N, N-dimethylacetamide (DMAc) 37g was added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 22 containing a polyimide precursor. A polyimide film 22 was obtained from the obtained composition 22 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例７］
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、Ｈ－ＢＰＤＡ２１．２ｇ（０．０６９ｍｏｌ）、ｍ－ＴＢ１４．７ｇ（０．０７０ｍｏｌ）、ＤＭＡｃ１０８ｇを加えた。この混合物を撹拌しながら昇温し８０℃で６時間反応させ、ポリイミド前駆体を含む組成物２３を得た。得られた組成物２３から実施例１と同様にポリイミドフィルム２３を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 7]
H-BPDA (21.2 g, 0.069 mol), m-TB (14.7 g, 0.070 mol), and DMAc (108 g) were added to a four-necked flask equipped with a refluxing nitrogen gas introduction tube, a condenser, and a stirrer. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 23 containing a polyimide precursor. A polyimide film 23 was obtained from the obtained composition 23 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例８］
　比較例７のＨ－ＢＰＤＡを６．８ｇ（０．０２２ｍｏｌ）、ｍ－ＴＢを４，４’－ジアミノジフェニルスルホン５．９ｇ（０．０２３ｍｏｌ）、ＤＭＡｃをＮＭＰ３７ｇに変更した以外は比較例７と同様の方法でポリイミド前駆体組成物２４及びポリイミドフィルム２４を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 8]
Comparative Example 7 and Comparative Example 7 except that 6.8 g (0.022 mol) of H-BPDA, 5.9 g (0.023 mol) of 4,4′-diaminodiphenylsulfone, and DMAc were changed to 37 g of NMP. The polyimide precursor composition 24 and the polyimide film 24 were obtained by the same method. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［比較例９］
　比較例２のＰＭＤＡを３．２ｇ（０．０１５ｍｏｌ）、６Ｆ－ｍ－ＴＢを８．８ｇ（０．０２７ｍｏｌ）、ＮＭＰを６９ｇに変更し、Ｈ－ＢＰＤＡをＢＰＤＡ４．４ｇ（０．０１５ｍｏｌ）、４，４’－ジアミノジフェニルスルホンを９，９－ビス（４－アミノフェニル）フルオレン０．９ｇ（０．００３ｍｏｌ）に変更した以外は比較例２と同様の方法でポリイミド前駆体組成物２５及びポリイミドフィルム２５を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Comparative Example 9]
PMDA of Comparative Example 2 was changed to 3.2 g (0.015 mol), 6F-m-TB was changed to 8.8 g (0.027 mol), NMP was changed to 69 g, H-BPDA was changed to 4.4 g (0.015 mol), The polyimide precursor composition 25 and the polyimide were prepared in the same manner as in Comparative Example 2 except that 4,4′-diaminodiphenylsulfone was changed to 0.9 g (0.003 mol) of 9,9-bis (4-aminophenyl) fluorene. Film 25 was obtained. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［参考例１］
　比較例６のＢＰＤＡを２，２－ビス（３，４－ジカルボキシフェニル）－１，１，１，３，３，３－ヘキサフルオロプロパン二無水物８．７ｇ（０．０２０ｍｏｌ）、６Ｆ－ｍ－ＴＢを６．４ｇ（０．０２ｍｏｌ）、ＤＭＡｃを４６ｇに変更した以外は比較例６と同様の方法でポリイミド前駆体組成物２６及びポリイミドフィルム２６を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。 [Reference Example 1]
BPDA of Comparative Example 6 was converted to 8.7 g (0.020 mol) of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 6F- A polyimide precursor composition 26 and a polyimide film 26 were obtained in the same manner as in Comparative Example 6, except that m-TB was changed to 6.4 g (0.02 mol) and DMAc was changed to 46 g. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2.
［参考例２］
　還流窒素ガス導入管、冷却器、攪拌機を備えた４つ口フラスコに、ＢＰＤＡ２．９ｇ（０．０１ｍｏｌ）、Ｈ－ＢＰＤＡ３．０ｇ（０．０１ｍｏｌ）、６Ｆ－ｍ－ＴＢ６．４ｇ（０．０２０ｍｏｌ）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）３７ｇを加えた。この混合物を撹拌しながら昇温し８０℃で６時間反応させ、ポリイミド前駆体を含む組成物２０を得た。得られた組成物２０から実施例１と同様にポリイミドフィルム２０を得た。実施例１と同様にポリイミドフィルムのＣＴＥ、Ｒｔｈ及びＹＩの測定を行った。結果を表２に示す。また、上記原料において、組成物の粘度が２００～６００ｃＰとなるようにジアミン化合物に対するテトラカルボン酸二無水物の比を調整し、組成物２７を得た。該比は表３に示す。
　実施例１と同様に、組成物２７をガラス基板上に塗布し、加熱した。得られたフィルムを剥離する際に、亀裂が生じ、フィルムを得ることができなかった。
　一方、組成物の粘度が２００～６００ｃＰとなるように、実施例７で用いた原料のジアミン化合物に対するテトラカルボン酸二無水物の比を調整し、組成物２８を得た。該比は表３に示す。
　実施例１と同様に、組成物２８をガラス基板上に塗布し、加熱した。得られたフィルムは亀裂等が発生せず、剥離することができた。 [Reference Example 2]
In a four-necked flask equipped with a reflux nitrogen gas introduction tube, a condenser, and a stirrer, 2.9 g (0.01 mol) of BPDA, 3.0 g (0.01 mol) of H-BPDA, 6.4 g of 6F-m-TB (0.020 mol) ), 37 g of N, N-dimethylacetamide (DMAc). The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 20 containing a polyimide precursor. A polyimide film 20 was obtained from the resulting composition 20 in the same manner as in Example 1. In the same manner as in Example 1, CTE, Rth, and YI of the polyimide film were measured. The results are shown in Table 2. In addition, the ratio of the tetracarboxylic dianhydride to the diamine compound was adjusted so that the viscosity of the composition in the raw material was 200 to 600 cP, whereby a composition 27 was obtained. The ratio is shown in Table 3.
In the same manner as in Example 1, the composition 27 was applied on a glass substrate and heated. When the obtained film was peeled off, cracks occurred and the film could not be obtained.
On the other hand, the ratio of the tetracarboxylic dianhydride to the raw material diamine compound used in Example 7 was adjusted so that the viscosity of the composition was 200 to 600 cP, whereby a composition 28 was obtained. The ratio is shown in Table 3.
In the same manner as in Example 1, the composition 28 was applied on a glass substrate and heated. The obtained film did not crack and could be peeled off.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　表２に示すように、本発明のポリイミドフィルム１～１５は、低線膨張係数及び低リタデーションの両立がなされていることが示された。一方、比較例に示すポリイミドフィルムは低線膨張係数及び低リタデーションの両立ができていないことが示された。 As shown in Table 2, it was shown that the polyimide films 1 to 15 of the present invention have both a low linear expansion coefficient and a low retardation. On the other hand, it was shown that the polyimide film shown in the comparative example cannot achieve both a low linear expansion coefficient and a low retardation.
　参考例２及び表３に示すように、屈曲部位の入っている組成物２８では、２００～６００ｃＰと低粘度化を行ってもフィルム化が可能であったが、屈曲部位の入っていない組成物２７では低粘度化を行うとフィルム化が困難であったことから、屈曲部位を有することで、幅広い粘度域で組成物を得ることができ、様々な塗布方法に適用可能となることが示された。 As shown in Reference Example 2 and Table 3, the composition 28 containing the bent portion could be formed into a film even when the viscosity was reduced to 200 to 600 cP, but the composition containing no bent portion was not included. 27, it was difficult to form a film when the viscosity was lowered. Therefore, it was shown that the composition can be obtained in a wide viscosity range by having a bent portion and can be applied to various coating methods. It was.
　本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１４年２月２１日出願の日本特許出願（特願２０１４－０３２１４７）、２０１４年６月２６日出願の日本特許出願（特願２０１４－１３１６６８）および、２０１５年１月６日出願の日本特許出願（特願２０１５－０００９９３）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is a Japanese patent application filed on February 21, 2014 (Japanese Patent Application No. 2014-032147), a Japanese patent application filed on June 26, 2014 (Japanese Patent Application No. 2014-131668), and an application filed on January 6, 2015. This is based on a Japanese patent application (Japanese Patent Application No. 2015-000993), the contents of which are incorporated herein by reference.
　本発明のポリイミド前駆体組成物は、コーティング材料、表面保護層、接着剤、デバイス用基板及び絶縁膜等に用いることができる。 The polyimide precursor composition of the present invention can be used for coating materials, surface protective layers, adhesives, device substrates, insulating films and the like.

Claims (6)

  1. 　テトラカルボン酸残基及びジアミン残基を含むポリイミドフィルムであって、
    　前記テトラカルボン酸残基及びジアミン残基の少なくともいずれか一方が屈曲部位を有し、
    　線膨張係数が６０ｐｐｍ／Ｋ以下であり、かつ、
    　リタデーションが２００ｎｍ以下であることを特徴とするポリイミドフィルム。     A polyimide film containing a tetracarboxylic acid residue and a diamine residue,
    At least one of the tetracarboxylic acid residue and the diamine residue has a bending site,
    The linear expansion coefficient is 60 ppm / K or less, and
    Retardation is 200 nm or less, The polyimide film characterized by the above-mentioned.
  2. 　フィルムの膜厚が１０μｍの際のイエローインデックスが、－１０以上、２０以下である、請求項１に記載のポリイミドフィルム。 The polyimide film according to claim 1, wherein the yellow index when the film thickness is 10 μm is −10 or more and 20 or less.
  3. 　ポリイミド前駆体及びポリイミドの少なくともいずれか一方を含む組成物であって、
    　前記ポリイミド前駆体及びポリイミドはテトラカルボン酸残基及びジアミン残基を含み、
    　前記テトラカルボン酸残基が下記式（１’）で表される部分構造、下記式（２）で表される部分構造及び下記式（４’）で表される部分構造を有し、
    　前記ジアミン残基が下記式（５）で表される部分構造を有し、
    　更に、前記テトラカルボン酸残基及びジアミン残基の少なくともいずれか一方が屈曲部位を有することを特徴とする組成物。
    Figure JPOXMLDOC01-appb-C000001
     　ただし式中の記号は以下の意味を表す。
    　Ｘ２は直接結合、２級若しくは３級炭素原子を有する結合、またはエーテル結合である。
    　Ｒ３及びＲ４はそれぞれ独立して、アルキル基、アルコキシ基、アミノ基及び水酸基からなる群より選ばれる官能基である。     A composition comprising at least one of a polyimide precursor and a polyimide,
    The polyimide precursor and polyimide include a tetracarboxylic acid residue and a diamine residue,
    The tetracarboxylic acid residue has a partial structure represented by the following formula (1 ′), a partial structure represented by the following formula (2), and a partial structure represented by the following formula (4 ′),
    The diamine residue has a partial structure represented by the following formula (5),
    Furthermore, at least one of the tetracarboxylic acid residue and the diamine residue has a bending site.
    Figure JPOXMLDOC01-appb-C000001
     However, the symbol in a formula represents the following meaning.
    X 2 is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
    R 3 and R 4 are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
  4. 　前記テトラカルボン酸残基中の前記式（４’）で表される部分構造を有するテトラカルボン酸残基の割合が、２ｍｏｌ％以上、９５ｍｏｌ％以下である、請求項３に記載の組成物。 The composition according to claim 3, wherein a ratio of a tetracarboxylic acid residue having a partial structure represented by the formula (4 ') in the tetracarboxylic acid residue is 2 mol% or more and 95 mol% or less.
  5. 　前記テトラカルボン酸残基中の前記式（１’）で表される部分構造を有するテトラカルボン酸残基及び前記式（２）で表される部分構造を有するテトラカルボン酸残基の和の割合が、５ｍｏｌ％以上、９５ｍｏｌ％以下である、請求項３又は４に記載の組成物。 The ratio of the sum of the tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) and the tetracarboxylic acid residue having a partial structure represented by the formula (2) in the tetracarboxylic acid residue The composition according to claim 3 or 4, wherein is 5 mol% or more and 95 mol% or less.
  6. 　前記テトラカルボン酸残基及びジアミン残基の和に対する、前記屈曲部位の割合が、０．１ｍｏｌ％以上、１５０ｍｏｌ％以下である、請求項３乃至５の何れか１項に記載の組成物。 The composition according to any one of claims 3 to 5, wherein a ratio of the bent part to a sum of the tetracarboxylic acid residue and the diamine residue is 0.1 mol% or more and 150 mol% or less.
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Cited By (16)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249116A (en) * 2005-03-08 2006-09-21 Fuji Photo Film Co Ltd Polyimide and optical film using the same
JP2007063417A (en) * 2005-08-31 2007-03-15 Fujifilm Corp Film and method for producing film, and film with gas-barrier layer, film with transparent electroconductive layer and image display device
JP2007161930A (en) * 2005-12-15 2007-06-28 Fujifilm Corp Optical film and image display
JP2011111596A (en) * 2009-11-30 2011-06-09 Kaneka Corp Manufacturing method of polyimide film, and polyimide film
JP2012233083A (en) * 2011-04-28 2012-11-29 Mitsubishi Chemicals Corp Device manufacturing method
JP2013082774A (en) * 2011-10-06 2013-05-09 Kaneka Corp Transparent polyimide film and production process thereof
JP2014019108A (en) * 2012-07-20 2014-02-03 Nippon Steel & Sumikin Chemical Co Ltd Transparent conductive film and polyimide film for producing the same
JP2014133887A (en) * 2012-12-14 2014-07-24 Mitsubishi Chemicals Corp Polyimide resin composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008163107A (en) * 2006-12-27 2008-07-17 Mitsubishi Gas Chem Co Inc Optical member
JP2012144603A (en) 2011-01-07 2012-08-02 Kaneka Corp Transparent polyimide film and method of manufacturing the same
JP5785018B2 (en) 2011-07-27 2015-09-24 株式会社カネカ Polyimide resin and optical film with improved film forming properties
TWI495404B (en) * 2013-06-21 2015-08-01 Chi Mei Corp Flexible substrate composition and flexible substrate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249116A (en) * 2005-03-08 2006-09-21 Fuji Photo Film Co Ltd Polyimide and optical film using the same
JP2007063417A (en) * 2005-08-31 2007-03-15 Fujifilm Corp Film and method for producing film, and film with gas-barrier layer, film with transparent electroconductive layer and image display device
JP2007161930A (en) * 2005-12-15 2007-06-28 Fujifilm Corp Optical film and image display
JP2011111596A (en) * 2009-11-30 2011-06-09 Kaneka Corp Manufacturing method of polyimide film, and polyimide film
JP2012233083A (en) * 2011-04-28 2012-11-29 Mitsubishi Chemicals Corp Device manufacturing method
JP2013082774A (en) * 2011-10-06 2013-05-09 Kaneka Corp Transparent polyimide film and production process thereof
JP2014019108A (en) * 2012-07-20 2014-02-03 Nippon Steel & Sumikin Chemical Co Ltd Transparent conductive film and polyimide film for producing the same
JP2014133887A (en) * 2012-12-14 2014-07-24 Mitsubishi Chemicals Corp Polyimide resin composition

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016158825A1 (en) * 2015-03-31 2018-01-11 旭化成株式会社 Polyimide film, polyimide varnish, product using polyimide film, and laminate
WO2017010566A1 (en) * 2015-07-16 2017-01-19 宇部興産株式会社 Polyamic acid solution composition and polyimide film
JP2017025163A (en) * 2015-07-17 2017-02-02 Jnc株式会社 Resin solution composition and polyimide film
JPWO2017051827A1 (en) * 2015-09-24 2018-03-22 旭化成株式会社 Polyimide precursor, resin composition and method for producing resin film
CN105273189A (en) * 2015-10-29 2016-01-27 阜新泓扬光电材料有限公司 Transparent polyimide film having ultraviolet obstruction function as well as preparation and application thereof
JP2019500487A (en) * 2015-12-21 2019-01-10 ドゥーサン コーポレイション Polyamic acid composition to which alicyclic monomer is applied, and transparent polyimide film using the same
JP2017115098A (en) * 2015-12-25 2017-06-29 ソマール株式会社 Polyimide copolymer and molded body using the same
WO2017111134A1 (en) * 2015-12-25 2017-06-29 ソマール株式会社 Polyimide copolymer and molded body using same
KR102390851B1 (en) 2015-12-25 2022-04-26 소마아루 가부시끼가이샤 Polyimide copolymer and molded article using same
CN108431087A (en) * 2015-12-25 2018-08-21 索玛尔株式会社 Polyimide copolymer and use its formed body
KR20180098253A (en) * 2015-12-25 2018-09-03 소마아루 가부시끼가이샤 Polyimide copolymer and molded article using the same
WO2017175869A1 (en) * 2016-04-07 2017-10-12 株式会社カネカ Polyimide resin, polyimide solution, film, and method for producing same
US10745519B2 (en) 2016-04-07 2020-08-18 Kaneka Corporation Polyimide resin, polyimide solution, film, and method for producing same
JP2017186473A (en) * 2016-04-07 2017-10-12 株式会社カネカ Film
JPWO2017195574A1 (en) * 2016-05-09 2019-03-07 三菱瓦斯化学株式会社 Polyimide resin and polyimide resin composition
WO2018208639A1 (en) * 2017-05-10 2018-11-15 E. I. Du Pont De Nemours And Company Low-color polymers for flexible substrates in electronic devices
JP2020528086A (en) * 2017-05-10 2020-09-17 デュポン エレクトロニクス インコーポレイテッド Low-color polymer for flexible substrates in electronic devices
KR20210013188A (en) 2018-06-22 2021-02-03 미쯔비시 케미컬 주식회사 Zeolite-containing polyimide resin composite material, zeolite-containing polyimide resin precursor composition, film, and electronic device
KR20210047858A (en) 2018-08-24 2021-04-30 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Polyimide resin, polyimide varnish and polyimide film
CN109281702A (en) * 2018-09-28 2019-01-29 黄旭东 A kind of preparation method preventing and treating spontaneous combustionof coal retardant
KR20210068394A (en) 2018-09-29 2021-06-09 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 Polyimide precursor and polyimide produced therefrom, and flexible device
KR20220123392A (en) 2019-12-26 2022-09-06 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Polyimide resin, polyimide resin composition, polyimide varnish and polyimide film
CN114181394A (en) * 2020-09-15 2022-03-15 航天特种材料及工艺技术研究所 Low-viscosity polyimide precursor solution and preparation method and application thereof

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TW201538572A (en) 2015-10-16
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JP5888472B2 (en) 2016-03-22

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