WO2015053237A1 - Composition de polyimide ainsi que film d'alignement et élément optique formés à l'aide de la composition de polyimide - Google Patents

Composition de polyimide ainsi que film d'alignement et élément optique formés à l'aide de la composition de polyimide Download PDF

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Publication number
WO2015053237A1
WO2015053237A1 PCT/JP2014/076734 JP2014076734W WO2015053237A1 WO 2015053237 A1 WO2015053237 A1 WO 2015053237A1 JP 2014076734 W JP2014076734 W JP 2014076734W WO 2015053237 A1 WO2015053237 A1 WO 2015053237A1
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Prior art keywords
polyimide
film
composition
anisotropic dye
alignment film
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PCT/JP2014/076734
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English (en)
Japanese (ja)
Inventor
美香 山口
二郎 杉山
政昭 西村
充哉 青葉
輝恒 大澤
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三菱化学株式会社
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Priority to KR1020167008988A priority Critical patent/KR20160068764A/ko
Priority to CN201480055445.8A priority patent/CN105612441A/zh
Priority to JP2015541576A priority patent/JP6428634B2/ja
Publication of WO2015053237A1 publication Critical patent/WO2015053237A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1096—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors containing azo linkage in the main chain
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a polyimide composition containing a polyimide having a specific structure and used for an alignment film for an anisotropic dye film.
  • the present invention also relates to an alignment film and an optical element formed using the polyimide composition.
  • the conventional liquid crystal display uses a polarizing film obtained by dyeing and stretching a polyvinyl alcohol (PVA) film or the like with a solution containing a dye, and orienting the dye in the drawing process, and therefore has low durability against humidity. . Therefore, establishment of a technique for an anisotropic dye film (polarizing film) using a dye that improves wet resistance and heat resistance is expected.
  • PVA polyvinyl alcohol
  • membrane is provided on a coating substrate and the pigment
  • an alignment film is obtained by applying a polyamic acid solution (polyimide precursor) to a substrate and heating (Patent Document 2).
  • a polyamic acid solution polyimide precursor
  • Patent Document 3 As the alignment film, an alignment film for liquid crystal has been conventionally studied, and it is disclosed that a liquid crystal alignment film is obtained by applying a polyamic acid solution to a substrate and heating.
  • polyimide has been studied as an optical film application.
  • Patent Documents 4 and 6 For example, in order to obtain a film having excellent heat resistance, transmittance, mechanical properties, and heat resistance, it is disclosed that a polyamic acid solution is heated after coating (Patent Documents 4 and 6). In addition, it is disclosed that a film is obtained by applying a polyimide solution having excellent solubility in organic solvents, heat resistance, dimensional stability, and transparency (Patent Document 5).
  • JP 2009-217011 Japanese Unexamined Patent Publication No. 2010-72521 Japanese Unexamined Patent Publication No. 2000-305088 Japanese Laid-Open Patent Publication No. 8-104750 Japanese Unexamined Patent Publication No. 2012-146905 Japanese Unexamined Patent Publication No. 2007-161930 Japanese Unexamined Patent Publication No. 2011-253054
  • Patent Document 1 discloses that an anisotropic dye film is produced by applying a dichroic dye to a polymer surface, but no consideration is given to providing an alignment film.
  • Patent Documents 2 and 3 disclose that a polyimide film is obtained by applying a polyamic acid solution on a substrate and performing a heat treatment at a high temperature of 200 ° C. or higher. Therefore, an alignment film for an anisotropic dye film cannot be formed on a material having a heat resistance of 200 ° C. or less. For example, a high-intensity color filter using a dye that has been developed in recent years has a problem that the luminance is lowered when processed at a high temperature of 200 ° C. or higher.
  • the alignment film using the polyamic acid as described above cannot be used as an alignment film for an anisotropic dye film.
  • the imidization reaction of the alignment film proceeds, and this water generated by water breaks the association of the anisotropic dye, resulting in deterioration of the anisotropic dye film.
  • the remaining amic acid site is hydrolyzed and the molecular weight of the polyimide is lowered, whereby the physical properties of the alignment film are changed and the alignment characteristics are deteriorated.
  • the remaining amic acid site is hydrolyzed to generate a highly reactive carboxylic acid end or amine end, thereby accelerating the deterioration and coloring of the dye and peripheral members in the anisotropic dye film.
  • Solvent molecules trapped in the amic acid moiety having a high affinity with the solvent are difficult to remove even during the drying process, and are volatilized as outgas during the subsequent process and storage, thereby degrading the device and peripheral members.
  • the remaining amic acid site absorbs the solvent or the like in the anisotropic dye film composition, and the alignment film swells. Further, by releasing the absorbed water, the association of the anisotropic dye is broken and the anisotropic dye film is deteriorated.
  • Patent Document 3 discloses that polyimide is used for the alignment film for liquid crystal, but no investigation is made as an alignment film for an anisotropic dye film.
  • the alignment film for liquid crystal aligns liquid crystal molecules of which one molecule is about several tens of thousands.
  • an alignment film for an anisotropic dye film needs to align about several hundreds of columns in which anisotropic dyes are associated. Due to the difference in size of the alignment material, the characteristics required for each alignment film are different, and the alignment film for liquid crystal cannot be diverted to the alignment film for anisotropic dye film.
  • Patent Documents 4 to 6 are optical film applications, and it is difficult to divert them to alignment films for anisotropic dye films.
  • Patent Documents 4 and 6 as in Patent Documents 2 and 3, in order to obtain a film, it is necessary to perform a heat treatment at a high temperature of 200 ° C. or higher after applying the polyamic acid solution. Further, according to the study by the present inventors, the polyimide used in Patent Document 5 has a high hydrophobicity, and there is a problem that the applicability to the anisotropic dye film composition is lowered.
  • An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a polyimide composition containing polyimide having excellent solubility in a solvent. Moreover, when a polyimide composition is excellent in applicability
  • the inventors of the present invention have excellent solubility in a solvent of a specific structure.
  • the polyimide composition can be applied. I found it excellent.
  • a polyimide composition containing a highly soluble polyimide it is not necessary to perform an imidization reaction at a high temperature after coating. That is, when forming the alignment film, it is only necessary to remove the solvent of the applied alignment film, and since it can be performed at a temperature lower than 200 ° C., the alignment film can be formed on a material such as a color filter. I found it. Further, it has been found that the alignment film obtained from the polyimide composition is excellent in surface treatment resistance such as rubbing and has high alignment characteristics of the anisotropic dye film. The present invention has been accomplished based on these findings.
  • a polyimide composition used for an alignment film for anisotropic dye film includes a polyimide and a solvent,
  • the said polyimide is represented by General formula (1),
  • the polyimide composition characterized by the above-mentioned.
  • X represents a tetravalent aliphatic hydrocarbon group having 5 or more carbon atoms
  • R 1 represents a divalent organic group having an aromatic ring
  • n represents an integer of 1 or more
  • a plurality of R 1 and X present in one molecule of the structure represented by the general formula (1) may be the same or different.
  • [2] The polyimide composition as described in [1] above, wherein the ratio of the number of elements forming an aromatic ring is 5% or more and 75% or less of the number of elements forming the main chain of the polyimide.
  • the polyimide having a specific structure of the present invention is excellent in solubility in a solvent, and the polyimide composition containing the polyimide and the solvent is excellent in coatability.
  • the polyimide composition of the present invention it is not necessary to perform an imidization reaction at a high temperature after coating, and only the solvent removal of the coating film can be performed at a low temperature, and an alignment film is formed on a material such as a color filter. can do.
  • the reason for the above effect is not clear, but is presumed as follows. Improve the solubility of the polyimide in the solvent by X of the polyimide represented by the general formula (1) contained in the polyimide composition of the present invention being a tetravalent aliphatic hydrocarbon group having 5 or more carbon atoms. Can do. Since the polyimide in the polyimide composition is difficult to deposit, the applicability of the polyimide composition is improved. In addition, since the polyimide composition of the present invention has high solubility in a solvent even when the imidization ratio of polyimide is high, it is not necessary to carry out an imidation reaction by heating after coating, and the solvent is used at a temperature of 200 ° C. or lower. It is possible to form an alignment film by removing.
  • X of the polyimide represented by the general formula (1) contained in the polyimide composition of the present invention being a tetravalent aliphatic hydrocarbon group having 5 or more carbon atoms. Can do. Since the polyimide in the
  • R 1 in the general formula (1) is a divalent organic group having an aromatic ring
  • the polyimide of the present invention has a rigid structure and linearity. Since the polyimide has linearity, the effect of surface treatment such as rubbing on the alignment film is more easily obtained. Due to the effect of the surface treatment such as rubbing, the linearity of the polyimide in the alignment film increases, and the alignment characteristics of the anisotropic dye film formed on the surface can be enhanced. Since R 1 is a divalent organic group having an aromatic ring, the R 1 moiety exhibits an electron donating property (donor).
  • the imide ring structure portion of polyimide exhibits an electron accepting property (acceptor)
  • the association property of the polyimide in the polyimide composition is obtained by the donor-acceptor interaction. Therefore, the alignment characteristic of the alignment film can be improved, and the alignment characteristic of the anisotropic dye film formed on the surface can be improved.
  • the polyimide of the present invention has a rigid structure and, as described above, the associative properties of the polyimide can be obtained, so that the surface treatment resistance is excellent. Therefore, it is possible to perform a strong surface treatment on the alignment film, and further improve the alignment characteristics of the polyimide.
  • the electron donating property refers to a state where the electron density of the ⁇ electron cloud on the aromatic ring is high
  • the electron accepting property refers to a state where the electron density is low.
  • the polyimide of the present invention is a combination of the above X and R 1 , the association of the polyimide in the polyimide composition by the donor-acceptor interaction can be improved while maintaining the solubility in a solvent. Therefore, the alignment characteristic of the obtained alignment film is improved, and the alignment characteristic of the anisotropic dye film can be enhanced.
  • the alignment film of the present invention has an aromatic ring and is excellent in interaction with an anisotropic dye having an aromatic ring, the alignment characteristics of the anisotropic dye film tend to be further improved.
  • the anisotropic dye has a relatively large association (column) structure of about several hundreds of pieces with which the anisotropic dye is associated.
  • the anisotropic dye hardly aligns following the alignment film. Therefore, in order to align the anisotropic dye, an alignment film having high alignment characteristics is required.
  • the polyimide having a specific structure according to the present invention has high alignment characteristics of the alignment film due to the above-described reasons. It is suitable for orienting the dye.
  • Polyimide composition The polyimide composition of this invention has the characteristics in containing the polyimide and solvent which are represented by General formula (1).
  • X represents a tetravalent aliphatic hydrocarbon group having 5 or more carbon atoms
  • R 1 represents a divalent organic group having an aromatic ring
  • n represents an integer of 1 or more
  • a plurality of R 1 and X present in one molecule of the structure represented by the general formula (1) may be the same or different.
  • the polyimide composition of the present invention may contain a plurality of polyimides as long as it contains the polyimide represented by the general formula (1).
  • the polyimide of the present invention does not need to be synthesized under the same reaction conditions, or only those having the same aromatic element ratio, imidization rate, and solubility. Mixtures prepared under different conditions and having different physical properties may be used.
  • the aromatic ring element ratio and imidation rate described below are average values of the polyimide constituting the polyimide composition.
  • the polyimide composition of this invention may contain components other than a polyimide, if it is a range which does not impair the effect of this invention.
  • the solvent used in the polyimide composition of the present invention is not particularly limited.
  • hydrocarbon solvents such as hexane, cyclohexane, and heptane
  • aromatics such as benzene, toluene, xylene, mesitylene, phenol, cresol, and anisole.
  • Solvents Halogenated hydrocarbon solvents such as carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene; Ether systems such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene Solvent: Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc .; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, die Glycol solvents such as lenglycol dimethyl ether and propylene glycol monomethyl ether acetate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polarities such as dimethyl
  • a hydrocarbon solvent an aromatic solvent, a glycol solvent, and an amide solvent.
  • toluene, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and anisole are preferably used.
  • Use of these solvents tends to improve the solubility of polyimide and facilitate the removal of the solvent when forming the alignment film.
  • the polyimide according to the present invention is not particularly limited as long as it includes a repeating unit containing at least an imide bond and has a skeleton having a specific structure represented by the general formula (1).
  • N is an integer of 1 or more, and there is no particular upper limit as long as the effect of the present invention is not impaired, but n is set so that the mass average molecular weight of the polyimide represented by the general formula (1) is in the range described later. It is preferable to define. These ranges are preferable because the solubility of the polyimide in the solvent, the viscosity of the polyimide composition, and the like tend to be in a range in which an alignment film can be easily formed.
  • R 1 and X present in a plurality in one molecule of the structure represented by the general formula (I) may be the same or different.
  • X in the general formula (1) represents a tetravalent aliphatic hydrocarbon group having 5 or more carbon atoms.
  • the aliphatic hydrocarbon group is cyclic or chain-like and may be a combination of these.
  • X has 5 or more carbon atoms, preferably 6 or more. Further, it is preferably 20 or less, more preferably 16 or less, and particularly preferably 14 or less. When the carbon number is within this range, the solubility of the polyimide in the solvent is improved, the polyimide composition is excellent in applicability, and heating after application tends to be performed at a low temperature.
  • the cyclic aliphatic hydrocarbon group or a group in which cyclic and chain aliphatic hydrocarbon groups are combined improves the solubility of the polyimide in the solvent and the applicability of the polyimide composition.
  • Examples of the chain aliphatic hydrocarbon group include an alkylene group which may have a substituent.
  • the chain aliphatic hydrocarbon group may be a straight chain or may have a branch.
  • Examples of the substituent that the alkylene group may have include an alkoxyl group having 1 to 4 carbon atoms and a trifluoromethyl group.
  • the cyclic aliphatic hydrocarbon group is a monocyclic ring, a condensed polycyclic ring, or a ring linked to each other directly or by a bridging member.
  • Specific examples include groups derived from alicyclic tetracarboxylic dianhydrides described below.
  • a single ring or a group in which single rings are connected to each other directly or by a crosslinking member is preferable because the solubility of polyimide in a solvent tends to be improved.
  • the monocyclic and condensed polycyclic aliphatic hydrocarbon groups share a single ring such as cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, and the two carbon atoms of the monocycle.
  • a condensed polycycle is mentioned.
  • the structure of the following formula (2), formula (3) or formula (4) is preferable, and the structure of formula (2) or formula (3) is particularly preferable.
  • the cyclic aliphatic hydrocarbon group in which monocyclic or condensed polycycles are directly or mutually linked by a bridging member has a structure represented by the following general formula (5), and the solubility of polyimide in a solvent is It is preferable because it is improved, the applicability of the polyimide composition is excellent, and heating after application tends to be performed at a low temperature.
  • X 1 and X 2 each independently represent a divalent cyclic aliphatic hydrocarbon group having 5 or more carbon atoms, and R 2 is a carbon that may have a direct bond or a substituent.
  • the divalent cyclic aliphatic hydrocarbon group for X 1 and X 2 is not particularly limited as long as it has 5 or more carbon atoms, but preferably has 10 or less carbon atoms, more preferably 8 or less. Furthermore, it is C5 and C6, the solubility to the solvent of a polyimide improves, it exists in the tendency which is excellent in the applicability
  • X 1 and X 2 may have a substituent, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a carboxy group, a sulfo group, an amino group Group, cyano group, nitro group, halogen atom and the like.
  • R 2 is a direct bond, an alkylene group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the following.
  • a direct bond is preferable because the solubility of polyimide in a solvent is improved, the applicability of the polyimide composition is excellent, and heating after application tends to be performed at a low temperature.
  • the substituent that the alkylene group of R 2 may have include an alkoxy group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen atom. And an alkylthio group having 1 to 5 carbon atoms, a trifluoromethyl group, and the like.
  • the following general formula (6) is preferable, and the following general formula (7) further improves the solubility of the polyimide in the solvent and improves the applicability of the polyimide composition. It is preferable because it is excellent and tends to be able to perform heating after coating at a low temperature.
  • R 3 in the general formula (6) has the same definition as R 2 in the general formula (5), and a preferred range is also the same.
  • R 1 represents any divalent organic group having an aromatic ring.
  • R 1 is not particularly limited as long as it is a divalent group having an aromatic ring, and the number of aromatic rings is not particularly limited.
  • groups other than an aromatic ring may be included.
  • the aromatic ring of the organic group may be a single ring, a condensed polycycle, and those in which these are connected to each other directly or by a bridging member.
  • the aromatic ring may be connected with a group other than the aromatic ring.
  • aromatic ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenylene ring, and a fluorene ring. These aromatic rings may have a substituent. Examples of the substituent which may be included include an alkyl group having 1 to 5 carbon atoms, a sulfo group, a cyano group, a trifluoromethyl group, and a halogen atom. Examples of the group other than the aromatic ring include an alkylene group having 1 to 4 carbon atoms, an alkenylene group having 1 to 4 carbon atoms, and a group represented by the following.
  • the alkylene group having 1 to 4 carbon atoms and the alkenylene group having 1 to 4 carbon atoms may have a substituent.
  • substituents which may be included include an alkoxy group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a carboxy group, a sulfo group, a cyano group, a nitro group, a halogen atom, and 1 to 5 carbon atoms. And the like.
  • connection position at which the aromatic ring is connected by a direct bond and a group other than the aromatic ring is not particularly limited, but the connection is preferably performed at a position that does not hinder the rigidity, association, and orientation characteristics of the polyimide molecule.
  • R 1 include a divalent group obtained by removing an amino group from a diamine compound, which is a raw material for polyimide represented by the general formula (1) described later.
  • the aromatic ring of R 1 is preferably a single ring from the viewpoint of solubility of polyimide in a solvent. Further, R 1 has 1 or more aromatic rings, and preferably 2 or more. The number of aromatic rings is preferably 6 or less, and more preferably 4 or less. When the number of aromatic rings is within the above range, solubility of polyimide in a solvent can be obtained, and further, rigidity and association of polyimide can be improved, and alignment characteristics and surface treatment resistance of the resulting alignment film can be improved. Tend to.
  • R 1 is particularly preferably a structure represented by the following formula (8), (9), (10) or (11).
  • R 10 in formula (9), R 11 to R 12 in formula (10), and R 13 to R 15 in formula (11) are each independently a linking group other than a divalent aromatic ring, specifically Represents the above-mentioned groups other than the aromatic ring of R 1 .
  • each aromatic ring of the formulas (8) to (11) may have an alkyl group having 1 to 5 carbon atoms, a sulfo group, a cyano group, a trifluoromethyl group, a halogen atom or the like as a substituent.
  • R 10 to R 15 are each an alkylene group having 1 to 4 carbon atoms or a group represented by the following, whereby the rigidity and associative properties of the polyimide are improved, and the orientation characteristics and surface resistance of the resulting orientation film are improved. Is preferable because of a tendency to improve.
  • At least one of R 10 , R 11 and R 12 , or at least one of R 13 to R 15 is —O—, which increases the electron donating property of R 1 , This is particularly preferable because the associating property of the polyimide by the action is improved and the orientation characteristics of the obtained orientation film tend to be improved.
  • X and R 1 The combination of X and R 1 described above is not particularly limited, but a combination in which X is a cyclic aliphatic hydrocarbon group and R 1 has a structure having a plurality of monocyclic aromatic rings is preferable.
  • X includes at least one structure represented by formulas (2) to (7) and R 1 includes at least one structure represented by formulas (8) to (9).
  • the polyimide of the present invention is not particularly limited as long as it contains the polyimide represented by the general formula (1), and a combination of a unit derived from tetracarboxylic dianhydride and / or a unit derived from a diamine compound is used in combination. It may be polymerized. Moreover, polyimides other than the polyimide represented by General formula (1) may be included in the polyimide composition.
  • the unit derived from the tetracarboxylic dianhydride to be copolymerized may contain other than aliphatic hydrocarbon groups having 5 or more carbon atoms as long as the effects of the present invention are not impaired.
  • aromatic ring such as a benzene ring and a naphthalene ring, a group in which an aromatic ring is directly bonded, a group in which a plurality of aromatic rings are connected with a linking group other than an aromatic ring, and the like.
  • the aromatic ring may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a sulfo group, a cyano group, a trifluoromethyl group, and a halogen atom.
  • the unit derived from the tetracarboxylic dianhydride to be copolymerized include groups derived from a tetracarboxylic dianhydride having an aromatic ring, which will be described later, as a polyimide raw material.
  • examples of the group derived from tetracarboxylic dianhydride having an aromatic ring include structures represented by the following formulas (12) to (14). The use of these is preferable because the rigidity and association of the polyimide are improved while maintaining the solubility of the polyimide in the solvent, and the alignment characteristics and surface treatment resistance of the resulting alignment film tend to be improved.
  • These aromatic rings may have a substituent. Examples of the substituent which may be included include an alkyl group having 1 to 5 carbon atoms, a sulfo group, a cyano group, a trifluoromethyl group, and a halogen atom.
  • R 15 represents an alkylene group having 1 to 4 carbon atoms, an alkenylene group having 1 to 4 carbon atoms, or a group represented by the following.
  • the connecting position of R 15 is not particularly limited and it is preferably connected at a position that does not interfere with the rigidity, associative and alignment properties of the polyimide molecule.
  • the proportion of units derived from anhydride is preferably 0.1 mol% or more, more preferably 1 mol% or more, preferably 99 mol% or less, more preferably 90 mol% or less.
  • the unit derived from the diamine compound to be copolymerized may not contain an aromatic ring as long as the effects of the present invention are not impaired.
  • examples thereof include a cyclic or chain aliphatic hydrocarbon group, a group connecting aliphatic hydrocarbon groups, and the like.
  • these groups may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a sulfo group, a cyano group, a trifluoromethyl group, and a halogen atom.
  • Specific examples include a divalent group obtained by removing an amino group from an aliphatic diamine compound having no aromatic ring, which will be described later, as a raw material for polyimide.
  • the proportion of units other than the units derived from the diamine compound used in the general formula (1) is preferably It is 0.1 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less.
  • the ratio of the number of elements forming an aromatic ring is preferably 75% or less, more preferably 65% or less, It is preferably 60% or less, particularly preferably 55% or less, and most preferably 50% or less. Further, it is preferably 5% or more, more preferably 7% or more, and further preferably 10% or more.
  • aromatic ring element ratio is in the above range, the polyimide is easily dissolved in the solvent, and when the polyimide composition is heated, precipitation or gelation tends not to occur.
  • the number of elements that form the main chain does not include the number of elements that form a hydrogen atom or a substituent that becomes a side chain.
  • the ratio of the aromatic ring element can be adjusted by adjusting the ratio of those having an aromatic ring with respect to the tetracarboxylic dianhydride and diamine compound (hereinafter sometimes referred to as “raw material monomer”) used as a raw material for polyimide synthesis. It can be a range.
  • the aromatic ring element ratio of the obtained polyimide and the alignment film containing the polyimide can be obtained by analyzing the composition of the raw material monomer obtained by solid NMR, IR, or the like. It can also be determined by analyzing the composition of the raw material monomer determined by gas chromatography (GC), 1 H-NMR, 13 C-NMR, two-dimensional NMR, mass spectrometry, etc. after dissolution with alkali.
  • the method of setting the aromatic ring element ratio of the polyimide within the above range includes tetracarboxylic dianhydride having an aromatic ring, tetracarboxylic dianhydride having no aromatic ring, diamine compound having an aromatic ring, and diamine having no aromatic ring.
  • the compound can be obtained by using the aromatic ring element in a ratio that falls within the above range.
  • the imidation ratio of the polyimide is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more. Moreover, there is no upper limit and the higher one is preferable.
  • the imidation ratio is in a specific range, the remaining amount of amic acid when the alignment film is formed can be suppressed, and a change with time such as hydrolysis tends to hardly occur.
  • the imidization ratio is in a specific range, the necessity of performing an imidization reaction (heating) when forming the alignment film is reduced, and the alignment film tends to be obtained by heating at a low temperature.
  • the imidation rate of this invention can be adjusted with the conditions of imidation in the manufacturing method mentioned later.
  • the imidation ratio indicates the ratio of imide bonds in the main chain of polyimide.
  • the imidization rate can be determined by a conventionally known method such as NMR, IR, and titration.
  • the imidation rate in the present invention is a value determined by IR.
  • Absorption strength of C C stretching vibration of sample at 100% imidization (A)
  • Absorption strength of C C stretching vibration of sample subjected only to solvent drying ( A ′)
  • the absorption strength (B ′) of CN stretching vibration is measured, and the imidation ratio of each polyimide composition can be calculated from the following formula (C).
  • Imidation ratio (B ′ / A ′) / (B / A) * 100 (C)
  • Preparation of 100% imidized sample is made by heating the sample to be measured at high temperature.
  • the heating temperature is usually 200 ° C. or higher, preferably 250 ° C. or higher, more preferably 300 ° C. or higher.
  • the drying temperature of a solvent can be determined according to the boiling point of the solvent used, it is usually 20 ° C. or higher, preferably 40 ° C. or higher, usually 200 ° C. or lower, and more preferably lower than the imidization reaction temperature.
  • the drying temperature is not too low, the solvent is sufficiently dried and unnecessary signals tend not to be observed during IR measurement. Further, since the drying temperature is not too high, the imidization rate does not change during drying, and an accurate imidization rate can be obtained.
  • soluble in a solvent means complete dissolution when polyimide is dissolved in a solvent constituting the composition at room temperature (25 ° C.).
  • the concentration for complete dissolution is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more.
  • a polyimide soluble in a solvent can be obtained by setting the ratio of the aromatic ring element in the main chain and the imidization ratio within the above ranges.
  • the concentration of the composition can be confirmed by using a conventionally known method as appropriate.
  • the solvent of the composition is dried using a method such as drying under reduced pressure, and the mass ratio before and after drying.
  • the composition can be concentrated by using a method such as distilling off the solvent under reduced pressure to determine solubility.
  • concentration of the composition is high, the measurement concentration can be 1% by 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
  • ethylene Glycol solvents such as glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate
  • aromatic solvents such as benzene, toluene, xylene, mesitylene, phenol, cresol, and anisole
  • hexane Hydrocarbon solvents such as cyclohexane and heptane
  • Hydrocarbon solvents such as cyclohexane and heptane
  • the ratio of the number of elements forming the aliphatic structure (hereinafter sometimes referred to as aliphatic element ratio) is 5 out of the number of elements forming the main chain of polyimide. % Or more, preferably 7% or more, particularly preferably 10% or more. Moreover, 60% or less is preferable, 50% or less is more preferable, 40% or less is further more preferable, and it is especially preferable to have 35% or less.
  • the number of elements that form the main chain does not include the number of elements that form a hydrogen atom or a substituent that becomes a side chain.
  • a tetracarboxylic dianhydride and a diamine compound having an aliphatic structure may be used in a ratio within an appropriate range.
  • the aliphatic structure includes both alicyclic and chain structures.
  • the weight average molecular weight (Mw) of a polyimide is not specifically limited, It is 1.0 * 10 ⁇ 3 > or more normally in polystyrene conversion, Preferably it is 5.0 * 10 ⁇ 3 > or more, More preferably, it is 1.0 * 10 ⁇ 4 > or more, Usually It is 1.0 ⁇ 10 6 or less, preferably 8.0 ⁇ 10 5 or less, more preferably 5.0 ⁇ 10 5 or less. These ranges are preferable because the solubility of the polyimide in the solvent, the viscosity of the polyimide composition, and the like tend to be in a range in which an alignment film can be easily formed.
  • the polystyrene-reduced weight average molecular weight can be determined by gel permeation chromatography (GPC).
  • the number average molecular weight (Mn) of the polyimide is not particularly limited, but is usually 5.0 ⁇ 10 2 or more, preferably 2.5 ⁇ 10 3 or more, more preferably 5.0 ⁇ 10 3 or more in terms of polystyrene, It is 5.0 ⁇ 10 4 or less, preferably 4.0 ⁇ 10 4 or less, more preferably 2.5 ⁇ 10 4 or less. This range is preferable in terms of solubility, solution viscosity, melt viscosity, and the like that are easy to handle in normal production equipment.
  • the number average molecular weight of polyimide can be measured by the same method as the above weight average molecular weight.
  • the molecular weight distribution of polyimide (PDI, (weight average molecular weight / number average molecular weight (Mw / Mn))) is usually 1 or more, preferably 1.1 or more, more preferably 1.2 or more, and usually 10 or less, preferably Is 9 or less, more preferably 8 or less.
  • the molecular weight distribution is preferably in this range in that a highly uniform composition can be obtained.
  • the molecular weight distribution of polyimide can be calculated
  • the polyimide according to the present invention is obtained by reacting a tetracarboxylic dianhydride and a diamine compound in an organic solvent.
  • Tetracarboxylic dianhydride examples of the tetracarboxylic dianhydride that is a raw material of the polyimide represented by the general formula (1) of the present invention include aliphatic tetracarboxylic dianhydrides having no aromatic ring. Examples of the aliphatic tetracarboxylic dianhydride include alicyclic tetracarboxylic dianhydrides and chain aliphatic tetracarboxylic dianhydrides.
  • alicyclic tetracarboxylic dianhydride examples include 3,3 ′, 4,4′-biscyclopentanetetracarboxylic dianhydride, 3,3 ′, 4,4′-biscyclohexanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tricyclo [6.4.0.02,7 Dodecane-1,8: 2,7-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,1 '-Biscyclohexane-3,3', 4,4'-tetracarboxylic dianhydride, 1,1'-oxybiscyclohexane-3,3 ', 4,4'-tetracarboxylic dianhydride, 1, 1'-sulfon
  • alicyclic tetracarboxylic dianhydrides are preferred.
  • These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
  • Examples of the diamine compound that is a raw material of the polyimide represented by the general formula (1) of the present invention include diamine compounds containing an aromatic ring.
  • Examples of the diamine compound having an aromatic ring include a diamine compound having one aromatic ring contained in the molecule, a diamine compound having two or more independent aromatic rings, and a diamine compound having a condensed aromatic ring.
  • a diamine compound having one aromatic ring contained in the molecule such as 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, etc .; 4,4 ′-(biphenyl- 2,5-diylbisoxy) bisaniline, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) Benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1, 3-bis (4-aminophenoxy) neopentane, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-
  • diamine compounds having an aromatic ring it is preferable to use a compound having two or more independent aromatic rings.
  • 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino-2,2 '-Dimethylbiphenyl and bis (4- (4-aminophenoxy) phenyl) sulfone are particularly preferable because they can maintain a solubility and obtain a polyimide having excellent dimensional stability.
  • These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
  • a tetracarboxylic dianhydride having an aromatic ring and / or an aliphatic diamine compound having no aromatic ring are used within a range not impairing the effects of the present invention. Polymerization may be performed.
  • the tetracarboxylic dianhydride having an aromatic ring includes a tetracarboxylic dianhydride having one aromatic ring in the molecule, a tetracarboxylic dianhydride having two or more independent aromatic rings, and condensation. Examples include tetracarboxylic dianhydrides having an aromatic ring.
  • tetracarboxylic dianhydride having one aromatic ring contained in the molecule such as pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride; 1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3, 3
  • tetracarboxylic dianhydride having one aromatic ring contained in the molecule and tetracarboxylic dianhydride having two or more independent aromatic rings.
  • biphenyltetracarboxylic dianhydride maintains the solubility of the polyimide in the solvent, the rigidity and associability of the polyimide are improved, and the orientation characteristics and surface treatment resistance of the resulting alignment film tend to be improved. Therefore, it is preferable.
  • aliphatic diamine compound having no aromatic ring examples include alicyclic diamine compounds and chain aliphatic diamine compounds.
  • alicyclic diamine compounds are preferred, and among them, 1,4-diaminocyclohexane and 1,3-bis (aminomethyl) maintain the solubility of the polyimide in the solvent while maintaining the rigidity of the polyimide. This is preferable because the associative property is improved and the orientation properties and surface treatment resistance of the resulting alignment film tend to be improved.
  • polyimide production method for example, a method of producing a polyamic acid as a precursor to obtain a polyimide (two-stage method), tetracarboxylic dianhydride A method (one-step method) for producing polyimide directly from a product and a diamine compound is used.
  • a polyamic acid from tetracarboxylic dianhydride and a diamine compound can be performed under 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 polyamic acid composition can be obtained by sequentially adding 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 tetracarboxylic dianhydride.
  • the concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the polyamic acid.
  • 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, based on the total liquid amount. Preferably it is 30 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 longer, preferably 2 hours or longer, usually 100 hours or shorter, preferably 24 hours or shorter. By carrying out the reaction under such conditions, a polyamic acid can be obtained at a low cost and in a 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 and heptane
  • aromatic solvents such as benzene, toluene, xylene, mesitylene, phenol, cresol and anisole
  • carbon tetrachloride Halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, fluorobenzene
  • ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methoxybenzene
  • acetone, methyl ethyl ketone, cyclohexanone Ketone solvents such as methyl isobutyl ketone
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ester
  • the polyamic acid solution thus obtained may be used as it is, or may be added to a poor solvent to be precipitated as a solid and then re-dissolved in another solvent to obtain a polyimide composition. .
  • the poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of polyimide resin.
  • Ether solvents such as diethyl ether or diisopropyl ether; Ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; Methanol , Alcohol solvents such as ethanol and isopropyl alcohol; and the like.
  • alcohol solvents such as isopropyl alcohol are preferable in that precipitates can be obtained efficiently, the boiling point is low, and drying is easy.
  • the solvent for dissolving the polyamic acid is not particularly limited.
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone
  • aprotic solvents such as dimethyl sulfoxide
  • Aromatic solvents such as benzene, toluene, xylene, mesitylene, phenol, cresol, anisole
  • glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate;
  • amide solvents, aromatic solvents and glycol solvents are preferred.
  • N, N-dimethylformamide, N, N-dimethylacetamide or N-methyl-2-pyrrolidone, anisole, ethylene glycol dimethyl ether and ethylene glycol monomethyl ether are preferred. These can be used alone, and can also be used as a mixture of two or more.
  • a polyimide composition can be obtained by dehydrating and cyclizing the above polyamic acid in the presence of a solvent.
  • imidation can be performed using any conventionally known method, examples thereof include thermal imidization by thermal cyclization and chemical imidization by chemical cyclization. These imidization reactions may be used alone or in combination.
  • the polyimide which is a specific imidation ratio of the present invention is a heating temperature, a heating time, a concentration of polyamic acid in a solvent, and, if an imidization accelerator is used, a kind, an addition amount, and an addition of an imidization accelerator It can be obtained by adjusting the timing of charging.
  • the solvent for imidizing the polyamic acid include the same solvents as those used in the reaction for obtaining the polyamic acid. The same or different solvents may be used for the polyamic acid production and the polyimide composition production.
  • water generated by the imidization reaction may be discharged out of the system in order to inhibit the ring closure reaction.
  • concentration of the polyamic acid 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, a polyimide having a controlled imidization rate can be obtained. In addition, polyimide can be produced with a solution viscosity that is high in production efficiency and easy to produce.
  • the imidization reaction temperature is not particularly limited as long as it does not depart from the gist of the present invention. It is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 220 ° C. or lower, particularly preferably 200 ° C. or lower. By performing within this range, it is possible to obtain a polyimide in which the imidization reaction proceeds efficiently and the imidization rate is controlled. Moreover, since side reactions other than imidation reaction are suppressed, it is preferable.
  • 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 carboxylic acid compounds, and heterocyclic compounds are preferable, and triethylamine, imidazole, and pyridine are particularly preferable because they tend to control the 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 the imidization accelerator used is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, particularly preferably 1 mol% or more based on the carboxyl group or ester group of the amic acid skeleton. 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. Furthermore, the reaction can be performed at a low cost and with a high yield.
  • 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 composition can be obtained by chemically imidizing a polyamic acid with a dehydrating condensing agent in the presence of a solvent.
  • the polyimide which is a specific imidization ratio of the present invention has a heating temperature, a heating time, a polyamic acid concentration in a solvent, a type of a dehydrating condensing agent, an amount of adding a dehydrating condensing agent, a timing for adding a dehydrating condensing agent, and the like. It can be obtained by adjusting.
  • the solvent used when imidizing the polyamic acid include the same solvents as mentioned in the synthesis of the polyamic acid in the above two-stage method.
  • 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 or halogenated compounds are preferable, and acid anhydrides are particularly preferable.
  • acid anhydrides are particularly preferable.
  • the imidation reaction proceeds efficiently, and a polyimide having a controlled imidation rate tends to be obtained.
  • 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 amic acid skeleton.
  • the imidization rate can be controlled.
  • the imidation rate can be controlled, production efficiency tends to be high, and the solution viscosity tends to be easy to manufacture.
  • the imidization reaction temperature is not particularly limited, the imidization reaction temperature is not particularly limited as long as it does not depart from the gist of the present invention, but is usually 0 ° C or higher, preferably 10 ° C or higher, more preferably 20 ° C or higher, Usually, it is 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, pressurization, or reduced pressure.
  • the atmosphere may be air or an inert atmosphere. Moreover, the above-mentioned tertiary amines etc. can also be added similarly to heat
  • a polyimide composition can be obtained directly from tetracarboxylic dianhydride and a diamine compound using a conventionally known method.
  • imidization is performed from synthesis of polyamic acid in a two-stage method to imidization without stopping the reaction or isolating an intermediate (polyamic acid).
  • the one-step method can also use the same reaction conditions as those of the heat imidization and chemical imidization.
  • tetracarboxylic dianhydride and diamine compound there are no particular limitations on the order and method of adding tetracarboxylic dianhydride and diamine compound to tetracarboxylic dianhydride and diamine compound.
  • a polyimide composition can be obtained by adding a tetracarboxylic dianhydride and a diamine compound to a solvent in this order and stirring at a temperature at which the reaction until imidization proceeds.
  • 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. is there.
  • 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.
  • 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. If the concentration in the solvent is too low, elongation of the molecular weight hardly occurs, and if it is too high, the viscosity becomes too high and stirring becomes difficult. Moreover, it exists in the tendency which can obtain the polyimide which controlled the imidation ratio because it is the said range. Examples of the solvent used in this reaction include the same solvents as those described above.
  • the obtained polyimide may be used as it is as a polyimide composition, or after being precipitated in a solid state by adding it to a poor solvent, it is redissolved in another solvent. It can also be used as a polyimide composition.
  • the poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of polyimide, but ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone, and methyl isobutyl ketone; methanol, Examples thereof include alcohol solvents such as ethanol and isopropyl alcohol. 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. Moreover, the solvent of the polyimide composition mentioned above is mentioned as a solvent which redissolves a polyimide.
  • an imidizing agent can be added to the polyimide composition in order to further increase the imidization rate when forming the alignment film.
  • the imidizing agent is not particularly limited as long as it promotes imidization, and the above-mentioned imidization accelerator can be used.
  • Preferred are carboxylic acid compounds or heterocyclic compounds, more preferred are heterocyclic compounds, and more preferred are 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, N, N-dimethylaminopyridine, nicotine.
  • addition of said compound may be added at the time of manufacture of a polyimide composition, and may be added just before application
  • a coupling agent such as a silane coupling agent or a titanium coupling agent can be added in order to adjust the adhesiveness to the coated body.
  • These compounds may be used individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.
  • 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.
  • 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.
  • 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.
  • these 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.
  • an optical element comprising an alignment film formed from the polyimide composition, an anisotropic dye film formed from the alignment film and a dye.
  • the alignment film of the present invention can be formed by applying the polyimide composition of the present invention to an object to be coated.
  • the application method is not particularly limited as long as it can form a layer having a uniform thickness.
  • a substrate including glass such as float glass or soda glass; plastic such as polyethylene terephthalate, polycarbonate, polyolefin, or the like can be used.
  • a functional silane-containing compound or a functional titanium-containing compound can be applied in advance to the surface of the substrate, which is an object to be coated. Further, ultraviolet treatment, plasma treatment, or the like can be performed.
  • the method for volatilizing the solvent of the polyimide composition is not particularly limited.
  • a solvent is volatilized by heating the to-be-coated body to which the polyimide composition is applied.
  • 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 in drying the solvent of the applied polyimide composition 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. is there. Further, it is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 150 ° C. or lower.
  • the solvent removal temperature is 20 ° C. or higher, it is preferable in that the solvent is sufficiently volatilized.
  • solvent removal temperature is 200 degrees C or less, the performance fall of each material at the time of forming alignment film in to-be-coated bodies, such as a low heat resistant material, for example, polyester resin, polyolefin resin, etc. can be suppressed.
  • the temperature for increasing the imidization rate is preferably 60 ° C or higher, more preferably 80 ° C or higher. Further, it is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 150 ° C. or lower. A heating temperature of 60 ° C. or higher is preferable because imidization proceeds efficiently and the remaining amount of amic acid that causes hydrolysis and the like decreases.
  • heating temperature is 200 degrees C or less, it exists in the tendency which can suppress the performance fall of each material at the time of forming alignment film in to-be-coated bodies, such as a low heat resistant material, for example, polyester resin, polyolefin resin.
  • the solvent removal temperature and the temperature for increasing the imidization rate may be different from each other or the same temperature.
  • each heating method may differ or may be the same.
  • the thickness of the alignment film obtained can be controlled by adjusting the coating amount of the polyimide composition.
  • the thickness of the alignment film is usually 1 nm or more, preferably 10 nm or more, and is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the thickness is 1 nm or more, the uniformity of the film thickness at the time of forming the alignment film is increased, and the alignment film can have sufficient alignment characteristics.
  • the hardness of the alignment film prepared from the polyimide composition of the present invention is such that the Vickers hardness at a film thickness of 2 ⁇ m is usually 10 or more, preferably 20 or more, more preferably 30 or more. Moreover, it is 100 or less normally, Preferably it is 80 or less, More preferably, it is 60 or less.
  • the Vickers hardness is in a specific range, scratches hardly occur on the alignment film, and application defects of the anisotropic dye film due to scratches on the alignment film tend to be prevented. Further, when a surface treatment such as a rubbing treatment of the alignment film is performed, the relaxation becomes slow and the surface treatment effect tends to be obtained.
  • the Vickers hardness can be measured as follows using a microhardness meter HM2000 (Fischer Instruments). As the indenter, a Vickers indenter is used. A load of 5 mN / ⁇ m 2 is applied at a load speed of 1.67 mN / sec. After holding for 5 seconds, the load is removed to obtain a Vickers hardness (Martens hardness ⁇ 0.0945).
  • the elastic deformation rate of the alignment film prepared with the polyimide composition of the present invention is usually 10% or more, preferably 15% or more, more preferably 18% or more, as determined by a microhardness meter at a film thickness of 2 ⁇ m. Yes, particularly preferably 20% or more. Moreover, it is 70% or less normally, Preferably it is 65% or less. When the elastic change rate of the alignment film is within this range, it becomes difficult to relax when surface treatment such as rubbing is performed, and the surface treatment such as rubbing can be maintained, and the orientation characteristics tend to be maintained. When rubbing is performed, the alignment film is less likely to be scraped or scratched by rubbing, and a uniform alignment film tends to be obtained.
  • the transmittance of the alignment film prepared from the polyimide composition of the present invention is usually 60% or more, preferably 70% or more, more preferably 80% or more on the longer wavelength side (visible region) from 400 nm. There is no particular upper limit on the transmittance, and a higher one is preferable.
  • An alignment film having a high light transmittance is preferably used in a device or the like that requires translucency. In particular, when used in a liquid crystal display, it is desirable that the transmittance of the blue region of the backlight is high, and specifically, it is preferable to have the above transmittance on a longer wavelength side than 420 nm.
  • the transmittance of the alignment film prepared from the polyimide composition of the present invention the total light transmittance according to JIS K 7136-1 is used.
  • a rubbing process in which the coated surface obtained above is rubbed in a certain direction with a roll wrapped with a cloth containing fibers such as nylon, rayon, and cotton, and a process of irradiating linearly polarized light. Etc. can be performed. By performing these treatments, an alignment film having higher alignment characteristics can be obtained. Among them, it is preferable to enhance the alignment characteristics by rubbing treatment in order to align the anisotropic dye film described later. When this rubbing treatment is performed on the alignment film and the anisotropic dye is aligned, it is necessary to perform the rubbing treatment more strongly than the liquid crystal alignment film. For this reason, the conventional alignment film for liquid crystal is scraped by rubbing, and there may be a defect in the anisotropic dye film due to process contamination due to scraping and damage to the alignment film caused by scraping.
  • the contact angle of the alignment film is usually 70 ° or less, preferably 60 ° or less, and more preferably 50 ° or less.
  • the contact angle is within an appropriate range, the dye solution tends to be uniformly applied without repelling the dye solution.
  • an anisotropic dye film composition is in a liquid crystal phase as a composition, and an anisotropic dye film formed after evaporation of the solvent has a high degree of orientation. It is preferable from a viewpoint of forming.
  • the state of the liquid crystal phase means that the liquid crystal phase is liquid as described on pages 1 to 16 of “Basics and Applications of Liquid Crystal” (Shoichi Matsumoto, Ryo Tsunoda, 1991). It is a liquid crystal state exhibiting both properties of crystal and crystal, and it means a nematic phase, a cholesteric phase, a numeric phase or a discotic phase. A nematic phase is particularly preferable.
  • curing agent, an additive, etc. may be mix
  • the anisotropic dye film composition may be in the form of a solution or gel.
  • the composition for anisotropic dye film may be in a state in which a dye or the like is dissolved or dispersed in a solvent.
  • the dye As the dye, a dichroic dye is usually used. Examples of the dichroic dye include a dye expressing a lyotropic liquid crystal, a dye expressing a thermotropic liquid crystal, and the like, and any of them may be used. In the present invention, the dye is preferably a dye having a liquid crystal phase for alignment control.
  • the dye having a liquid crystal phase means a dye that exhibits lyotropic liquid crystallinity in a solvent, and may or may not exhibit a liquid crystal phase when the composition for an anisotropic dye film is formed. Although it is good, the liquid crystal phase is preferable as described above.
  • the dye used in the present invention may be soluble in water or an organic solvent so that the anisotropic dye film composition exhibits a liquid crystal phase and is used for a wet film-forming method described later.
  • Particularly preferred is water solubility.
  • Further preferred are compounds having an inorganic value smaller than the organic value as defined in “Organic Conceptual Diagram-Fundamentals and Applications” (Yoshio Koda, Sankyo Publishing, 1984).
  • the molecular weight is preferably 200 or more, particularly preferably 300 or more, more preferably 1500 or less, and particularly preferably 1200 or less.
  • water-soluble means that the compound is usually dissolved in water at 0.1% by mass or more, preferably 1% by mass or more at room temperature.
  • composition for anisotropic dye film of the present invention only one kind of dye may be used, or two or more kinds may be used in combination.
  • two or more types are combined, in order for the anisotropic dye film composition to exhibit a liquid crystal phase, it is sufficient that at least one type is a pigment that exhibits a liquid crystal phase.
  • the dye examples include azo dyes, stilbene dyes, cyanine dyes, phthalocyanine dyes, and condensed polycyclic dyes (perylene and oxazine dyes).
  • the dye used in the present invention is not particularly limited, and the following known dyes can be used.
  • the dye include, for example, Japanese Unexamined Patent Publication No. 2006-0799030, Japanese Unexamined Patent Publication No. 2010-168570, Japanese Unexamined Patent Publication No. 2007-302807, Japanese Unexamined Patent Publication No. 2008-081700, Japanese Unexamined Patent Publication No. 09-230142, Japan 2007-722211, Japan 2007-186428, Japan 2008-69300, Japan 2009-169341, Japan JP 2009-161722, JP 2009-173849, JP 2010-039154, JP 2010-180314, JP 2010-266769, JP No. 2010-031268, Japanese Unexamined Patent Publication No.
  • JP 2012-194365 JP include dyes described in Japanese Patent 2011-016920 Patent Publication.
  • the above dye is suitable as a dye for an anisotropic dye film formed by a wet film forming method, has low wavelength dispersibility, and has a high degree of polarization and dichroic ratio. Moreover, since the said pigment
  • An azo dye means a dye having at least one azo group. The number of azo groups in one molecule is preferably 2 or more, and preferably 6 or less. Further, 4 or less is more preferable. When the azo group is in an appropriate number, the wavelength dispersion is low, a color tone having absorption in a wide range in the visible region is obtained, and the production tends to be easy.
  • each of the disazo, trisazo and tetrakisazo dyes having the structure of the following general formula (A) in the form of a free acid is compatible with the alignment film formed from the polyimide composition of the present invention. It is preferable because an anisotropic dye film having excellent molecular orientation and a high degree of molecular orientation can be obtained. Furthermore, the dye having the structure of the general formula (A) is preferable because it has a low wavelength dispersibility and a color tone having absorption in a wide range in the visible region is obtained.
  • E 1 represents an arbitrary organic group
  • R 20 and R 21 each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent.
  • p and q each independently represent an integer of 1 or more and 5 or less, and the sum of p and q represents 2 or more and 6 or less.
  • each of the disazo, trisazo and tetrakisazo dyes having the structure of the following general formula (B) in the form of a free acid is formed from the polyimide composition of the present invention.
  • An anisotropic dye film having excellent compatibility with the film and showing a high degree of molecular orientation can be obtained, which is more preferable.
  • dye which has a structure of general formula (B) is especially preferable from the color dispersion which has a low wavelength dispersion property and has absorption in a visible region widely.
  • E 2 represents an arbitrary organic group
  • R 22 and R 23 each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent.
  • the dye in the present embodiment may be used in the form of a free acid, or a part of the acid group may have a salt form. Further, a salt-type dye and a free acid-type dye may be mixed. Moreover, when it is obtained in a salt form at the time of production, it may be used as it is or may be converted into a desired salt form.
  • a salt-type exchange method a known method can be arbitrarily used, and examples thereof include the following methods.
  • a strong acid such as hydrochloric acid is added to an aqueous solution of a dye obtained in a salt form, the dye is acidified in the form of a free acid, and then the dye is added with an alkaline solution having a desired counter ion (for example, an aqueous lithium hydroxide solution).
  • a method of neutralizing acidic groups and salt exchange is performed.
  • a neutral salt eg, lithium chloride
  • An aqueous solution of a dye obtained in a salt form is treated with a strongly acidic cation exchange resin, and the dye is acidified in the form of a free acid, and then an alkali solution having a desired counter ion (for example, an aqueous lithium hydroxide solution). ) To neutralize the acidic group of the dye and perform salt exchange. 4) A method of performing salt exchange by allowing an aqueous solution of a dye obtained in a salt form to act on a strongly acidic cation exchange resin previously treated with an alkaline solution having a desired counter ion (for example, an aqueous lithium hydroxide solution).
  • the acidic group of the dye in the present embodiment is a free acid type or a salt type depends on the pKa of the dye and the pH of the aqueous dye solution.
  • the salt type include salts of alkali metals such as Na, Li and K, ammonium salts which may be substituted with alkyl groups or hydroxyalkyl groups, and organic amine salts.
  • the organic amine include a lower alkyl amine having 1 to 6 carbon atoms, a hydroxy-substituted lower alkyl amine having 1 to 6 carbon atoms, a carboxy-substituted lower alkyl amine having 1 to 6 carbon atoms, and the like.
  • the type is not limited to one type, and a plurality of types may be mixed.
  • the above dyes can be used alone, but two or more of these may be used in combination, and dyes other than the above exemplified dyes may be blended and used to such an extent that the orientation is not lowered. Thereby, anisotropic dye films having various hues can be produced.
  • Examples of blending pigments when blending other pigments include C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 34, C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 142, C.I. I. Direct Yellow 132, C.I. I. Acid Yellow 25, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Orange 79, C.I. I. Acid Orange 28, C.I. I. Direct Red 39, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Acid Red 37, C.I. I. Direct Violet 9, C.I.
  • anthraquinone compound may be blended in the anisotropic dye film composition of the present invention in accordance with the methods described in Japanese Patent Application Publication No. 2007-199333 and Japanese Patent Application Publication No. 2008-101154. Furthermore, the methods described in Japanese Unexamined Patent Publication No. 2006-3864 and Japanese Unexamined Patent Publication No. 2006-323377 may be used.
  • the composition for anisotropic dye film of the present invention has a temperature of 5 ° C. for an anisotropic dye film composition and 0.01% after strain application as described in Japanese Patent Application Laid-Open No. 2007-179933.
  • the defect of the anisotropic dye film may be controlled by setting the time until the relaxation elastic modulus G after 1 second is reduced to 1/10 to 0.1 second or less.
  • the cation is 0.9 equivalent or more and 0.99 equivalent or less and the strongly acidic anion is 0.02 equivalent or more with respect to the acidic group of the azo compound in the composition for anisotropic dye film. , 0.1 equivalent or less is included.
  • the solvent is not particularly limited as long as it dissolves or disperses the above compound.
  • water, a water-miscible organic solvent, or a mixture thereof is suitable because the dye easily forms an association state such as a lyotropic liquid crystal in the solvent.
  • the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and glycerin, glycols such as ethylene glycol and diethylene glycol, and cellosolves such as methyl cellosolve and ethyl cellosolve, or a mixture of two or more.
  • a solvent is mentioned.
  • water, methanol, and ethanol are preferable, and water is particularly preferable because it promotes association between highly organic portions such as an aromatic ring of the dye.
  • the concentration of the dye in the composition for anisotropic dye film is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 50% by mass, although it depends on the film forming conditions. Hereinafter, it is more preferably 30% by mass or less. If the dye concentration is excessively low, the association of the dyes in the composition becomes insufficient, and the anisotropic dye film obtained cannot obtain anisotropy such as a sufficient degree of polarization and dichroic ratio. If it is too high, the viscosity becomes so high that it is difficult to apply a uniform thin film, or the dye may precipitate in the composition for anisotropic dye film.
  • the anisotropic dye film composition may further contain additives such as a surfactant, a leveling agent, a coupling agent, and a pH adjuster as necessary. Depending on the additive, wettability, applicability and the like may be improved.
  • a surfactant any of anionic, cationic and nonionic properties can be used.
  • the addition concentration is not particularly limited, but is usually sufficient as the concentration in the anisotropic dye film composition as an amount that is sufficient to obtain the added effect and does not inhibit the orientation of the molecule. 0.01 mass% or more is preferable and 0.1 mass% or more is further more preferable. Moreover, 5 mass% or less is preferable, 1 mass% or less is more preferable, 0.5 mass% or less is especially preferable.
  • a known pH adjuster such as acid / alkali is added to the anisotropic dye. It may be added either before or after mixing the components of the film composition or during mixing.
  • “Additive for Coating”, Edited by J. Known additives described in Bieleman, Willy-VCH (2000) can also be used.
  • an anisotropic dye film is preferably formed on the alignment film of the present invention by a wet film formation method.
  • the wet film-forming method referred to in the present invention is a method in which an anisotropic dye film composition is applied to an alignment film by any method, and a dye is aligned and laminated on a substrate through a process of drying a solvent. is there.
  • the anisotropic dye film composition when the anisotropic dye film composition is formed on the substrate, the dye itself self-associates in the anisotropic dye film composition or in the process of drying the solvent. Causes orientation in a small area.
  • an anisotropic dye film having desired performance can be obtained by orienting in a certain direction in a macro region.
  • This is different from the method based on the principle that a so-called polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye and stretched, and the dye is oriented only by a stretching process.
  • the external field includes the influence of the orientation treatment layer previously applied on the base material, shear force, magnetic field, etc., and these may be used alone or in combination.
  • the process of forming the composition for an anisotropic dye film on the substrate, the process of aligning by applying an external field, and the process of drying the solvent may be performed sequentially or simultaneously.
  • the method for applying the anisotropic dye film composition on the substrate in the wet film forming method include a coating method, a dip coating method, an LB film forming method, a known printing method, and the like.
  • the present invention preferably uses a coating method.
  • the anisotropic dye film can be formed by applying the anisotropic dye film composition to the alignment film.
  • the orientation direction of the anisotropic dye film is usually coincident with the application direction, but may be different from the application direction.
  • the orientation direction of the anisotropic dye film is, for example, a transmission axis or absorption axis of polarized light in the case of an anisotropic dye film, and a fast axis or in the case of a retardation film. It is the slow axis.
  • the anisotropic dye film in the present embodiment functions as a polarizing film or retardation film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, as well as film forming processes and coatings.
  • a composition containing an applied body (substrate or the like) or an organic compound (colorant or transparent material) it can be functionalized as various anisotropic films such as refractive anisotropy and conduction anisotropy.
  • the method for applying the anisotropic dye film composition to obtain the anisotropic dye film is not particularly limited.
  • Yuji Harasaki Coating Engineering
  • Methods described on pages 253 to 277 supervised by Kunihiro Ichimura, “Creation and Application of Molecular Coordination Materials” (CMC Publishing Co., Ltd., published on March 3, 1998), pages 118 to 149
  • Examples of the method include coating on the coated body by a slot die coating method, a spin coating method, a spray coating method, a bar coating method, a roll coating method, a blade coating method, a curtain coating method, a fountain method, and a dip method.
  • the slot die coating method is preferable because an anisotropic dye film with high uniformity can be obtained.
  • the anisotropic dye film composition that expresses a preferable lyotropic liquid crystal phase as the above-mentioned anisotropic dye film composition by the above-described application method, It is considered that the dye is oriented by the influence of the orientation treatment of the orientation film or the like previously applied on the substrate and the shearing force applied to the anisotropic dye film composition at the time of application.
  • the method for supplying the composition for anisotropic dye film and the supply interval when applying the composition for anisotropic dye film continuously are not particularly limited, but the operation of supplying the coating liquid becomes complicated, or the coating liquid When the anisotropic dye film is thin, especially while supplying the composition for the anisotropic dye film continuously, the coating film thickness may vary at the start and stop of It is desirable to apply.
  • the speed at which the composition for anisotropic dye film is applied is usually 1 mm / second or more, preferably 5 mm / second or more, more preferably 10 mm / second or more. Moreover, it is 1000 mm / sec or less normally, Preferably it is 200 mm / sec or less. It is. If the coating speed is too small, the anisotropy of the anisotropic dye film may be lowered. On the other hand, when too large, there exists a possibility that it cannot apply
  • coating temperature of the composition for anisotropic dye films it is 0 degreeC or more and 80 degrees C or less normally, Preferably it is 40 degrees C or less. Moreover, the humidity at the time of application
  • the film thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 50 nm or more as a dry film thickness. On the other hand, it is preferably 30 ⁇ m or less, more preferably 1 ⁇ m or less. When the film thickness of the anisotropic dye film is in an appropriate range, there is a tendency that uniform orientation of molecules and a uniform film thickness can be obtained in the film.
  • the anisotropic dye film may be insolubilized.
  • Insolubilization means a treatment step that increases the stability of the film by controlling the elution of the compound from the anisotropic dye film by reducing the solubility of the compound in the anisotropic dye film.
  • an ion with a lower valence is replaced with an ion with a higher valence (for example, a monovalent ion is replaced with a polyvalent ion), or an organic molecule or polymer having a plurality of ionic groups.
  • a replacement process is listed.
  • the obtained anisotropic dye film is treated by a method described in Japanese Patent Application Laid-Open No. 2007-241267, etc. to obtain an anisotropic dye film insoluble in water. It is preferable from the viewpoint of ease and durability.
  • the transmittance of the anisotropic dye film in the visible light wavelength region is preferably 25% or more. 35% or more is more preferable, and 40% or more is particularly preferable.
  • permeability What is necessary is just an upper limit according to a use. For example, when used for a liquid crystal display, it is preferably 50% or less.
  • the orientation characteristic of the anisotropic dye film can be expressed by the degree of polarization.
  • the degree of polarization is such that the single transmittance is 36% or more and is usually 95% or more, preferably 98% or more, and more preferably 99% or more. Moreover, the higher the degree of polarization, the better. The maximum value is 100%.
  • the degree of polarization is not less than the above numerical value, it is useful as the following optical element, particularly as a polarizing element.
  • Each transmittance is not particularly limited as long as it has the same wavelength, and any wavelength may be selected depending on the purpose.
  • Polarization degree (P) (%) ⁇ (Ty ⁇ Tz) / (Ty + Tz) ⁇ 1/2 ⁇ 100 Tz: transmittance for polarized light in the direction of the absorption axis of the anisotropic dye film Ty: transmittance for polarized light in the direction of the polarization axis of the anisotropic dye film
  • anisotropic dye or the composition for anisotropic dye film can be directly added to the polyimide composition of the present invention to be used as an anisotropic dye film.
  • Each condition in this case can be performed in the same manner as the method for forming the anisotropic dye film.
  • the optical element of the present invention is a polarizing element that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc., utilizing retardation of light absorption, a retardation element, refractive anisotropy, conductive anisotropy, etc. It is an element having a function. These functions can be appropriately adjusted depending on the film forming process and the selection of a composition containing an object to be coated (substrate or the like) or an organic compound (pigment or transparent material). In the present invention, it is preferably used as a polarizing element.
  • the polarizing element of the present invention has any other film (layer) as long as it has an alignment film and an anisotropic dye film composition on an object to be coated (substrate or the like). It may be a thing. For example, it can be produced by forming an anisotropic dye film composition on the surface of the alignment film.
  • the polarizing element of the present invention is an overcoat layer, an adhesive layer or an antireflection layer, an alignment film, a function as a retardation film, a function as a brightness enhancement film, if necessary, in addition to the alignment film and the anisotropic dye film.
  • Layers with various functions such as a function as a reflection film, a function as a transflective film, a layer with optical functions such as a diffusion film, etc. are laminated by coating or bonding, and used as a laminate. May be.
  • These layers having an optical function can be formed, for example, by the following method.
  • the layer having a function as a retardation film is subjected to stretching treatment described in, for example, Japanese Patent Application Laid-Open No. 2-59703, Japanese Patent Application Laid-Open No. 4-230704, or Japanese Patent Application Laid-Open No. 7-230007. It can be formed by performing the treatment described in the above.
  • the layer having a function as a brightness enhancement film may be formed with micropores by a method as described in, for example, Japanese Patent Application Laid-Open No. 2002-169025 or Japanese Patent Application Laid-Open No. 2003-29030, or It can be formed by overlapping two or more cholesteric liquid crystal layers having different central wavelengths of selective reflection.
  • the layer having a function as a reflective film or a transflective film can be formed using a metal thin film obtained by vapor deposition, sputtering, or the like.
  • the layer having a function as a diffusion film can be formed by coating the protective layer with a resin solution containing fine particles.
  • the layer having a function as a retardation film or an optical compensation film can be formed by applying and aligning a liquid crystal compound such as a discotic liquid crystal compound or a nematic liquid crystal compound.
  • the anisotropic dye film in the present embodiment is used as an anisotropic dye film or the like for various display elements such as LCDs and OLEDs, an alignment film directly on the surface of the electrode substrate or the like constituting these display elements
  • An anisotropic dye film can be formed, or a substrate on which an alignment film and an anisotropic dye film are formed can be used as a constituent member of these display elements.
  • the optical element of the present invention can be directly formed on a highly heat-resistant coated body (substrate or the like) such as glass, a highly heat-resistant polarizing element can be obtained, so that a liquid crystal display or an organic electroluminescence display can be obtained.
  • it can be suitably used for applications that require high heat resistance, such as liquid crystal projectors and in-vehicle display panels.
  • ⁇ Aromatic ring element ratio It calculated from the ratio of the aromatic tetracarboxylic anhydride and diamine compound in a raw material monomer.
  • the polyimide composition containing the reaction solution was determined as “x” when the solid content (insoluble polyimide resin) was precipitated at room temperature, and “ ⁇ ” when completely dissolved.
  • ⁇ Vickers microhardness meter measurement> The solid concentration of the synthesized polyimide compositions 1 to 3 was diluted to 15% by weight to obtain a coating solution. 7 This coating solution was applied to a glass substrate using a spin coater, heated at 80 ° C. for 10 minutes, and further heated at 140 ° C. for 1 hour. The film thickness at this time was 2 ⁇ m. Using this film, a Vickers micro hardness tester HM2000 (manufactured by Fischer Instruments) is used. The indenter is a Vickers indenter. A load of 5 mN / ⁇ m 2 is applied at a load speed of 1.67 mN / sec and held for 5 seconds. Thereafter, the load was removed, and Vickers hardness (Martens hardness ⁇ 0.0945), elastic change rate: (total deformation ⁇ plastic deformation) / total deformation ⁇ 100 were obtained.
  • HM2000 manufactured by Fischer Instruments
  • Example 2 Synthesis was performed in the same manner as in Example 1 except that 2,2-bis (4- (4-aminophenoxy) phenyl) propane of Example 1 was changed to 4.6 g of 4,4′-diaminodiphenyl ether. A polyimide composition 2 was obtained. About the obtained polyimide composition 2, it evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 3 Example 2, except that 2,2-bis (4- (4-aminophenoxy) phenyl) propane in Example 1 was changed to 4.8 g of 4,4′-diamino-2,2′-dimethylbiphenyl. Synthesis was performed in the same manner to obtain a polyimide composition 3. About the obtained polyimide composition 3, it evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 4 In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer, 13.3 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromerit 1.5 g of acid dianhydride, 14.0 g of 3,4-diaminodiphenyl ether, 86 g of N-methyl-2-pyrrolidone and 17.3 g of toluene were added. The mixture was heated with stirring and reacted at 160 to 170 ° C. for 13 hours to obtain a polyimide composition 4. About the obtained polyimide composition 4, it evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 5 To 15.714 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride of Example 4, 3,714 ', 4,4'-biscyclohexanetetracarboxylic dianhydride was added 3,4-diaminodiphenyl ether. 25.949 g of bis (4- (4-aminophenoxy) phenyl) sulfone, 1.243 g of pyromellitic dianhydride, 82 g of N-methyl-2-pyrrolidone, and 16.3 g of toluene were changed. The polyimide composition 5 was obtained by synthesizing in the same manner as in Example 4. The obtained polyimide composition 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 1,2,4,5-cyclohexanetetracarboxylic dianhydride of Example 4 to 9.982 g of 1,2,3,4-cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride to 0 g, A polyimide composition 6 was obtained by synthesizing in the same manner as in Example 4, except that the amount of 3,4-diaminodiphenyl ether was changed to 10.12 g, N-methyl-2-pyrrolidone was changed to 60 g, and toluene was changed to 12 g. It was. The obtained polyimide composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 The 1,2,4,5-cyclohexanetetracarboxylic dianhydride of Example 4 was added to 12.63 g of 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride.
  • Example 4 except that melitric anhydride was changed to 1.0 g, 3,4-diaminodiphenyl ether was changed to 9.66 g, N-methyl-2-pyrrolidone was changed to 70.10 g, and toluene was changed to 10.5 g.
  • Example 7 was synthesized in the same manner as above to obtain a polyimide composition 7. About the obtained polyimide composition 7, it evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 2 The 1,2,4,5-cyclohexanetetracarboxylic dianhydride of Example 4 was changed to 4.2 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and pyromellitic dianhydride was changed to 0 g. Same as Example 4 except that 3,4-diaminodiphenyl ether was changed to 4.8 g of 4,4-diamino-2,2-dimethylbiphenyl, 27 g of N-methyl-2-pyrrolidone, and 5.4 g of toluene. Thus, a polyimide composition 9 was obtained. About the obtained polyimide composition 9, it measured by the method similar to Example 1. FIG. The polyimide composition 9 was not soluble. Moreover, since it was not soluble, the imidation ratio could not be measured. The results are shown in Table 1.
  • Examples 8 to 14 Using polyimide compositions 2 to 7 synthesized in Examples 2 to 7, alignment films 1 to 7 were produced as follows. Further, rubbing treatment was performed on each alignment film, and the presence or absence of scratches or scraping on the film after rubbing was confirmed with the naked eye. The compositions 8 and 9 of Comparative Examples 1 and 2 were not soluble and the polyimide was deposited, so that the coating could not be performed and an alignment film could not be obtained.
  • Polyimide compositions 2 and 3 were diluted to 4% by mass with a coating solvent (N, N-dimethylacetamide) to obtain a coating solution.
  • composition for anisotropic dye film 20 parts by mass of the azo compound represented by formula (I) and 1 part by mass of the compound represented by formula (II) are added to 79 parts by mass of water and stirred. After being dissolved, the solution was filtered to remove insoluble matter, thereby obtaining an aqueous dye solution (anisotropic dye film composition).
  • the above-mentioned anisotropic dye film composition is applied to the polyimide alignment film produced by the above method with an applicator (manufactured by Horita Seisakusho Co., Ltd.) with a gap of 4 ⁇ m, and then naturally dried to obtain an anisotropic dye film. It was.
  • the anisotropic dye film is formed by applying the above anisotropic dye film composition to the polyimide alignment film produced by the above method by applying it using a die coater having a slot width of 50 ⁇ m, and then naturally drying. Obtained.
  • the optical performance was evaluated by the single transmittance and the degree of polarization of the anisotropic dye film.
  • the single transmittance and the degree of polarization were determined using a spectrophotometer equipped with a Gram-Thomson polarizer (product name “RETS-100” manufactured by Otsuka Electronics Co., Ltd.).
  • the linearly polarized measuring light was incident on the anisotropic dye film and the transmittance was measured.
  • the degree of polarization at 620 nm which is the maximum absorption wavelength of the anisotropic dye film, was calculated by the following equation.
  • Polarization degree (P) (%) ⁇ (Ty ⁇ Tz) / (Ty + Tz) ⁇ 1/2 ⁇ 100
  • Tz Transmittance with respect to polarized light in the direction of the absorption axis of the anisotropic dye film
  • Ty Transmittance with respect to polarized light in the direction of the polarization axis of the anisotropic dye film Evaluation was performed as follows from the single transmittance and the degree of polarization.
  • Examples 1 to 7 (polyimide compositions 1 to 7) were all soluble.
  • the alignment films 1 to 7 obtained by using the compositions 2 to 7 were free from scratches or scraping due to rubbing, and were shown to have excellent surface treatment resistance. Further, since the alignment films 1 to 7 are excellent in the optical characteristics of the anisotropic dye film, it can be seen that the alignment films of the present invention have high alignment characteristics.
  • the present invention can be used in any industrial field.
  • the present invention can be suitably used in a field where an alignment film having a high distribution characteristic is required.
  • a display, etc. it can be particularly suitably used in a field where an optical element is required.

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Abstract

　L'invention concerne une composition de polyimide utilisée dans un film d'alignement pour un film de pigment anisotrope, la composition de polyimide étant caractérisée en ce que la composition de polyimide comprend un polyimide et un solvant et le polyimide est représenté par la formule générale (1). (Dans la formule générale (1), X représente un hydrocarbure aliphatique tétravalent ayant au moins 5 atomes de carbone, R1 représente un groupe organique divalent ayant un noyau aromatique, n représente un nombre entier égal ou supérieur à 1 et, lorsque n est égal ou supérieur à 2, une pluralité de R1 et de X présents dans une molécule de la structure représentée par la formule générale (1) peuvent chacun être identiques ou différents).
PCT/JP2014/076734 2013-10-07 2014-10-06 Composition de polyimide ainsi que film d'alignement et élément optique formés à l'aide de la composition de polyimide WO2015053237A1 (fr)

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KR1020167008988A KR20160068764A (ko) 2013-10-07 2014-10-06 폴리이미드 조성물, 상기 폴리이미드 조성물을 사용하여 형성된 배향막 및 광학 소자
CN201480055445.8A CN105612441A (zh) 2013-10-07 2014-10-06 聚酰亚胺组合物、使用上述聚酰亚胺组合物形成的取向膜及光学元件
JP2015541576A JP6428634B2 (ja) 2013-10-07 2014-10-06 ポリイミド組成物、前記ポリイミド組成物を用いて形成された配向膜及び光学素子

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WO2022004856A1 (fr) * 2020-07-02 2022-01-06 住友化学株式会社 Film optique
JP2022511459A (ja) * 2018-11-30 2022-01-31 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド 配向性に優れたポリイミドフィルムから製造されるグラファイトシートおよびその製造方法
JP2023043032A (ja) * 2021-09-15 2023-03-28 シャープディスプレイテクノロジー株式会社 偏光板及び表示装置

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KR102161673B1 (ko) 2017-09-07 2020-10-05 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
KR102162501B1 (ko) 2017-09-08 2020-10-06 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
JP2019049661A (ja) * 2017-09-11 2019-03-28 シャープ株式会社 配向膜、液晶パネル及び液晶パネルの製造方法
CN114628675B (zh) * 2021-11-08 2023-08-15 万向一二三股份公司 一种三元锂电池正极材料及其制备方法

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WO2022004856A1 (fr) * 2020-07-02 2022-01-06 住友化学株式会社 Film optique
JP2023043032A (ja) * 2021-09-15 2023-03-28 シャープディスプレイテクノロジー株式会社 偏光板及び表示装置

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