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WO1997002233A1 - Nouveaux anhydrides de l'acide carboxylique, composes amines, resines polyimides, et leur procede de fabrication - Google Patents

Nouveaux anhydrides de l'acide carboxylique, composes amines, resines polyimides, et leur procede de fabrication Download PDF

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Publication number
WO1997002233A1
WO1997002233A1 PCT/JP1996/001887 JP9601887W WO9702233A1 WO 1997002233 A1 WO1997002233 A1 WO 1997002233A1 JP 9601887 W JP9601887 W JP 9601887W WO 9702233 A1 WO9702233 A1 WO 9702233A1
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Prior art keywords
group
formula
substituent
anhydride
aromatic
Prior art date
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PCT/JP1996/001887
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English (en)
Japanese (ja)
Inventor
Yutaka Honda
Iwao Fukuchi
Nobuo Miyadera
Toshihiko Kato
Perminder Singh Johar
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Hitachi Chemical Company, Ltd.
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Application filed by Hitachi Chemical Company, Ltd. filed Critical Hitachi Chemical Company, Ltd.
Priority to AU63196/96A priority Critical patent/AU6319696A/en
Publication of WO1997002233A1 publication Critical patent/WO1997002233A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • 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
    • 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 liquid crystal alignment film, particularly a rubbingless liquid crystal alignment film (a liquid crystal alignment film that retains the alignment ability in a non-rubbing manner) or a nonlinear optical material such as an optical waveguide or a wavelength conversion element.
  • the present invention relates to a novel carboxylic acid anhydride, an amide compound, a polyimide resin, and a method for producing the same, which can be usefully used as a carboxylic acid anhydride.
  • liquid crystal alignment film in a liquid crystal display element a liquid crystal alignment film obtained by treating a resin thin film formed on a substrate by a rubbing method has been mainly used.
  • the rubbing method liquid crystal molecules are aligned in a certain direction on the film surface by rubbing a resin film formed on a substrate with a cloth covered with a number of fibers on a velvet. This is a simple process.
  • a diazomin dye is applied to the polyimide liquid crystal alignment film, and a cell is prepared by aligning the liquid crystal in a certain direction by a rubbing method. When this cell is irradiated with polarized laser light, the liquid crystal is aligned. Gibbons and colleagues reported that the direction changes in the direction perpendicular to the direction of the electric field of the illuminated polarized light (Nature, Vol. 31, 51, pp. 49, 1). 9 9 1 year).
  • the liquid crystal molecules can be switched between the vertical alignment and the parallel alignment only by light irradiation, and It was reported that the direction of parallel orientation could be changed by deflected irradiation (Ichimura: Applied Physics, Vol. 62, No. 10, p. 998, p. 1993, etc.).
  • Fibers may fall off the fabric, static electricity will be generated during rubbing, making it easier for trash to adhere, and those fibers and trash may be rubbed against the substrate and scratched, causing fibers and trash to adhere. If the panel is assembled as it is, the cell gap will be defective, a process of cleaning the substrate after rubbing is required to avoid this, and the alignment performance will be degraded by cleaning depending on the material of the alignment film. There's a problem. Also, in an active matrix type liquid crystal display element, the switching element may be destroyed due to static electricity. Furthermore, when the substrate has irregularities or the substrate area is large, it is difficult to rub uniformly.
  • the purpose of the present invention is not to use a rubbing method, but also to use a non-rubbing method (rubbingless alignment method). And a novel monomeric carboxylic anhydride and an amine compound which are used as raw materials for producing the polyimide resin.
  • the present invention firstly relates to an azo group-containing carboxylic anhydride.
  • the azo group-containing carboxylic anhydride of the present invention has the following general formula
  • L represents hydrogen, a hydroxyl group, or mono-OCOR (where R is an alkyl group or an aromatic group),
  • a r a shows one acid anhydride group aromatic group even if also Tsuhoka substituents even rather small on the aromatic ring. ].
  • a r' is a Kaoru incense ring constituting A r 2 and A r 3 , Benzene, naphthalene, biphenyl, thiophene, benzo [b] thiophene, naphtho [2,3-b] thiophene, thiazulene, franc, pyran, benzo [b] Furan, isobenzofuran, chromene, xanthen, phenoxatin, 2H—pyrrol, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine , Indoleidine, isoindole, 3H — indole, indole, 1H — indazole, purine, 4H — quinolizine, isoquinoline, quinoline, phthala
  • Aromatic ring ⁇ ⁇ ', ⁇ ⁇ ' is a substituent on and Alpha gamma 3, acid anhydride group, a hydroxyl group, an alkyl group, an alkenyl group, an alkyl Okishi group, an alkylthio group, an alkyl sulfoxide group, ⁇ Rukirususoreho G, arsoalkyl silyl olenoyl, alkyl silyl oleoxy, alkylamino, dialkylamino, alkylarylamino, aryl, aryloxy, arylthio, arylthio Arylsulfoxide, arylsulfonyl, arylsylyl, arylsyloxyl, dia Release amino, acyl, acyloxy, acylthio, acylsulfoxyd, acylsulfon, acylsilyl, acylsilyloxy, acylamino
  • the azorequil includes saturated hydrocarbon groups such as methylenole, ethyl, propyl, butyl, and pentyl; saturated cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; vinyl and acetyl. Unsaturated hydrocarbon groups such as lilyl, cyclopentenyl, cyclohexenizole, benzyl, triphenylmethyl, etc .; perfluorinated compounds such as trifluoromethyl, pentafunolelochinole, heptafunolelopropyl, etc. (2) Alkyl and their isomers.
  • phenyl examples include phenyl, naphthyl, biphenyl, thiophenisole, benzo [b] thiophenisole, naphthol.
  • acyl examples include alkylcarbonyl groups such as honoleminore, acetyl, propionyl, and butanoinole, and arylbenzenes such as benzoyl, alkenylbenzoyl, and alkyloxybenzoyl.
  • Zol group methansulfonyl, ethanesulfonyl, ⁇ .
  • sulfonyl groups such as rat norenensulfonyl and the like, and their heterologous groups.
  • alkyl group for R in the formula (A-II) examples include saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, and pentyl, and saturated hydrocarbon groups such as cyclopentyl and cyclohexyl. ⁇ -shaped hydrocarbon group, vinyl, aryl, cyclopentenyl, cyclohexenyl, Unsaturated hydrocarbon groups such as benzyl, triphenylmethyl, etc .; trifluoroalkyl, pentafluorophenol, heptafluoro propyl, etc., monofluoroalkylfures, and isomers thereof. There is.
  • the aromatic group of R in the formula (A-II) includes phenyl, naphthyl, biphenyl, thiophenyl, benzo [b] thiophenyl, naphthyl [2, 3-b] thiophenil, thiazlenyl, franyl, piranyl, benzo [b] franyl, isobenzofuranyl, chromensol, Xanthenil, Phenoxatin, 2H—Pirroiliré, Pilornaceinol, Imidazoll ⁇ l ⁇ l l ⁇ l ⁇ , Villal ⁇ l ⁇ l ⁇ l l ⁇ l, Pil ⁇ ,, ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ 3, 3H- — — ⁇ 3 ⁇ ⁇ , 3 , 1H-Indazo-Izore, Prin-no
  • L has the same meaning as in formula (A-I), and the hydrogen atom on the benzene ring may be substituted with a substituent.
  • the substituents on the benzene ring are the same as those described above for the aromatic rings Ar 2 and Ar 3 .
  • a hydrogen atom on the benzene ring may be substituted with a substituent.
  • Is represented. Specific examples of such a compound are the following formula (A-IIla1) and formula (A-Ilia2).
  • the azo group-containing carboxylic anhydride of the formula (A-I) has the following formula (A-IV)
  • L represents hydrogen, a hydroxyl group, or ⁇ C ⁇ R (where R is an alkyl group or an aromatic group),
  • Ar 1 and Ar 2 each represent an aromatic group which may have a substituent on the aromatic ring.
  • Ar 3 represents an aromatic group having at least one acid anhydride group on the aromatic ring and optionally having a substituent
  • Q represents a halogen atom.
  • the compound can be produced by adding an acid halide or an acid anhydride represented by the following formula and subjecting it to a condensation reaction in a solvent in the presence of a base.
  • the amount of the formula (A-V) or the formula (A-V ') used in the above condensation reaction is such that the molar ratio is 1 to 2 with respect to the formula (A-IV). It is preferable to adjust it.
  • Examples of the solvent used include N, N-dimethylacetamide, N, N-dialkylformamide and other N, N-dialkylacylamide solvents, getyl ether, diisopropyl ether, and tetrahydrofuran.
  • Examples include ether solvents such as drofuran, aromatic hydrocarbon solvents such as benzene and toluene, alkane solvents such as hexane and heptane, dimethyl sulfoxide, dimethyl sulfone, and the like.
  • the azo group-containing carboxylic anhydride of the formula (A-IV) is represented by Ar 2 -NH 2 (A-VI II)
  • a compound represented by the following formula can be produced by adding a compound represented by the following formula and subjecting it to an azokapping reaction.
  • a solvent for the above reaction water is usually used.
  • the azo coupling reaction described above is a well-known method [New Laboratory Chemistry Lecture, Vol. 14 (II) (Maruzen Co., Ltd., published on February 20, 1980), page 112
  • the reaction is carried out at a low temperature (preferably 10 ° C. or less) in an atmosphere of an inert gas such as nitrogen.
  • an inert gas such as nitrogen.
  • pyridine, triethylamine, dimethylaniline, and other amides sodium hydroxide, sodium hydroxide, and hydroxide are used.
  • Alkali metal hydroxide or alkaline earth metal hydroxide such as calcium, hydrogenated alkaline metal or hydrogenated alkaline earth metal such as sodium hydride, potassium hydride, calcium hydride
  • Alkali metals such as, lithium, sodium and potassium can be used, and the use of amines or alkali metals is preferred.
  • the amount of the amide or alkali metal used is preferably 1 to 3 mol per 1 mol of the produced halogen acid. If the amount is less than 1 mol, the capture of halogen acid is insufficient, and if it is more than 3 mol, the yield may be reduced due to side reactions.
  • the azo coupling reaction is usually performed in an organic solvent.
  • the solvent include N, N—dimethylacetamide, N, N—dialkylacylamide solvents such as N, N-dimethylformamide, getyl ether, diisopropyl ether, and tetrahydrofuran.
  • ether solvents such as drofuran
  • aromatic hydrocarbon solvents such as benzene and toluene
  • anolecan solvents such as hexane and heptane
  • dimethyl sulfoxide Uses N, N-dialkylacylamide solvent. Two or more of these may be mixed as long as they are compatible with each other. It is preferable to use a sufficiently dehydrated organic solvent. If water is present in the reaction system, the yield may decrease due to the decomposition reaction.
  • the azo group-containing carboxylic anhydride of the general formula (A-I ') has the following formula
  • R represents an alkyl group or an aromatic group. Is reacted in the presence of a base to give the azo group-containing carboxylic anhydride of the formula (A-II).
  • the molar ratio of the formula (A-I ') and the formula (A-VII) used in the above condensation reaction is preferably adjusted so as to be 1 to 0.5 in molar ratio.
  • Examples of the solvent used include N, N-dimethylacetamide, N, N-dialkylformamide such as N, N-dimethylformamide, getyl ether, diisopropyl ether, and tetraethyl acetate.
  • ether solvents such as hydrofuran, aromatic hydrocarbon solvents such as benzene and toluene, alkane solvents such as hexane and heptane, dimethyl sulfoxide, dimethyl sulfone, and the like.
  • Examples include triethylamine, pyridine, N, N-dimethylaminopyridine, N, N-diisopropylpropylamine, DBU, and the like.
  • Ar 3 has the same meaning as in formula (II-I), and Q represents a halogen atom.
  • Q represents a halogen atom.
  • the amount of the formula (A-V) or (A-V ') used in the condensation reaction is adjusted to be 2 or more in molar ratio with respect to the formula (A-VI).
  • Solvents used include N, N-dimethylformamide, N, N-dimethylformamide, and other N, N-dialkylacylamide media, geethylether, diisopropyl ether, tetraethyl ether, and the like.
  • Solvents such as ether solvents such as lahydrofuran, aromatic hydrocarbon solvents such as benzene and toluene, alkane solvents such as hexane and butane, and solvents such as dimethyl sulfoxide and dimethyl sulfone.
  • ether solvents such as lahydrofuran
  • aromatic hydrocarbon solvents such as benzene and toluene
  • alkane solvents such as hexane and butane
  • solvents such as dimethyl sulfoxide and dimethyl sulfone.
  • bases triethylamine, pyridin, N, N-dimethylaminopyridine, N, N-diisoprop
  • An azo group-containing dihydroxy aromatic ring compound of (HO) 2 -A r '-N N-A r 2 (A-VI) or a salt thereof,
  • the ratio (molar ratio) of the amount of the compound of the formula (A-VI) and the amount of the compound of the formula (A-V) or (A-V ') as a raw material ) Is adjusted to 1 to 0.5, or if the reaction solvent is a hardly soluble solvent that does not easily dissolve the monoester product (although the raw material is dissolved), then the monomer represented by the general formula (A-I ') Ester forms are predominantly formed.
  • the amount of the formula (A-V) or (A-V '), which is a raw material may be larger than the amount of the formula (A-VI) (for example, the molar ratio
  • the monoester forms predominantly as a precipitate.
  • Examples of the solvent when using the poorly soluble product solvent include N, N-dimethylalkylacetamide, N, N-dialkylacylamide such as N, N-dimethylformamide, and getyl ether.
  • Ether solvents such as diisopropyl ether and tetrahydrofuran, aromatic hydrocarbon solvents such as benzene and toluene, alkane solvents such as hexane and heptane, dimethyl sulfoxide and dimethyl From sulfone, etc., select as appropriate according to the target compound.
  • the L force of the general formula (A-I) obtained as described above Hydrogen or carboxylic anhydride, which is a COR, is usually purified by ripening and dissolving it in a dehydrated solvent containing anhydrous acetic acid or acetic anhydride, followed by gradual cooling and crystallization. Can be.
  • carboxylic anhydrides of the general formula (A-I) wherein L is a hydroxyl group [formula (A-I ')] are treated without heating in acetic anhydride or a dehydrating solvent containing acetic anhydride. Then, it can be purified by a method such as treating it with an organic solvent that does not dissolve it and extracting and removing impurities.
  • the present invention also provides the following general formula (B—I)
  • a r '-O-D-A r'-X 2 X 2 -A r 2 (B-I) (wherein, Ar 'and Ar 2 may have a substituent on the aromatic ring. Represents an aromatic group
  • Ar 4 represents an aromatic group having at least one amino group on the aromatic ring and optionally having a substituent
  • D is one (CR 'R 2) n- X l -, or one (CR' R 2 CR 1 R z - X 1) n- are shown (but, R 'and R 2 are hydrogen, or a substituent
  • An alkyl group which may have, X 1 is 0 or S, and n is an integer of 2 to 20),
  • X 2 is N or CR 3 (where R 3 represents hydrogen or an alkyl group which may have a substituent), and the two X 2 may be the same or different.
  • R 3 represents hydrogen or an alkyl group which may have a substituent
  • Ar ′ in the formula (B-I) is an aromatic group having at least one amino group on the aromatic ring and optionally having a substituent.
  • substituents on the aromatic rings are the same as the aromatic ring and substituents mentioned for a r ', ⁇ ⁇ 2 and Alpha gamma 3 of the previous general formula (A- I).
  • R 3 is hydrogen or an alkyl group which may have a substituent.
  • Same alkyl group i.e., saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, etc .; saturated cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; vinyl, aryl and cyclopentenyl Unsaturated hydrocarbon groups such as cyclohexenyl, benzyl, triphenylmethyl, etc., and parafluoroarylalkyl such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and the like, or isomers thereof. Is mentioned.
  • Ar 1 is a phenyldiyl group which may have a substituent on an aromatic ring
  • Ar 2 is a substituent on an aromatic ring
  • Ar 4 is a phenyl group which may have a substituent in addition to two amino groups on the aromatic ring, wherein D is — (CH 2 ) n— — Is a compound of the following formula (B — la) ⁇ • (CH 2 ) n-
  • X 2 is N or CR 3 (where R 3 represents hydrogen or an alkyl group which may have a substituent.), And two X 2 may be the same or different. And n represents an integer of 2 to 20, and hydrogen on the benzene ring may be substituted with a substituent.
  • a r has the same meaning as in formula (B-I). And a salt thereof, or a salt thereof.
  • Y (leaving group) is a methansulfonyloxy group, a trifluoromethansulfonyloxy group, a benzenesulfonyloxy group, a norabromobenzenesulfonyl group.
  • a sulfonyloxy group such as a niloxy group or a nor-toluenesulfonyloxy group, or a halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group can be used.
  • the reaction of the compound of the formula (B-III) or a salt thereof with the compound of the formula (B-II) is performed in an organic solvent.
  • the compound of the formula (B-II) is preferably used in an amount equivalent to or more than the compound of the formula (B-III) or a salt thereof, and the reaction atmosphere is intended to prevent a decrease in yield due to the decomposition reaction. Therefore, anhydrous (or low) oxygen and anhydrous conditions are preferred.
  • the compound of the formula (B-III) is first treated with a metal salt-forming reagent in an organic solvent, and then the metal salt of a phenolic hydroxyl group is treated. Then, the metal salt is reacted with the compound of the formula (B-II).
  • organic solvent examples include amide solvents such as N, N-dimethylacetamide, N, 'N-dimethylformamide, N-methyl-2-pyrrolidone, getyl ether, diisopro- ide and the like.
  • Ether solvents such as pyruether and tetrahydrofuran; aromatic hydrocarbon solvents such as benzene and toluene; alkane solvents such as hexane and heptane; and dimethyl sulfoxide.
  • amide solvents, and these organic solvents are preferably anhydrous.
  • Metal salt forming reagents include lithium hydride, potassium hydride, sodium hydride, calcium hydride, and other metal hydrides, methyllithium, butyllithium, sec—butisorrelli. Alkali metals such as tium and t-butylsolelithium, metal amides such as sodium amide, lithium diisopropyl amide, lithium bistrimethylsilyl amide, etc., potassium, sodium, etc. There are metals such as lithium.
  • the metal salt-forming reagent is used in an amount equal to or more than the equivalent of the compound of the formula (B-III), preferably, in an amount equal to or more than the equivalent of the compound of the formula (B-III) + 1 mol.
  • the reaction temperature is not particularly limited, but is preferably from 0 ° C to the boiling point of the solvent.
  • the salt is hydrofluoric acid, hydrochloride, bromate, oxalate, nitrate, sulfate, borate, or maleate If it is an acid salt such as oxalate, acetate, propionate, or the like, the salt is treated with a metal salt-forming reagent in an organic solvent to form a phenolic hydroxyl group metal salt. Then, the metal salt is reacted with the compound of the formula (B-II) in an organic solvent.
  • organic solvent the same organic solvents as those described above can be used.
  • metal salt forming reagent the same reagents as described above can be used.
  • the amount of the metal salt-forming reagent is at least the equivalent of the salt-forming acid, preferably at least the equivalent of the salt-forming acid + 1 mol.
  • the reaction temperature is not particularly limited, but is preferably from 0 ° C to the boiling point of the solvent.
  • the salt when a salt of the compound of the formula (B-III) is used, the salt is a lithium salt, a potassium salt, a sodium salt, in the case of a metal salt of a phenolic hydroxyl group such as a calcium salt, these metal salts are directly reacted with the compound of the formula (B-II) in an organic solvent.
  • the organic solvent the same organic solvents as those described above can be used.
  • the reaction temperature is not particularly limited, but is preferably from 0 ° C to the boiling point of the solvent.
  • the reaction product can be purified by appropriately combining one or more of various commonly used purification methods such as a chromatography method, a recrystallization method, and a sublimation method. At this time, it is desirable that the purification operation be performed in a short time under light shielding and in an inert gas atmosphere.
  • the carboxylic anhydride or amide compound thus obtained is used as a raw material (monomer) for producing polymers, especially polyimide resins such as polyimides and polyamide imides.
  • polyimide resins such as polyimides and polyamide imides.
  • a polyimide resin containing the carboxylic anhydride and / or the amine compound of the present invention can be obtained.
  • the present invention provides at least one compound selected from the group consisting of an azo group-containing sulfonic anhydride represented by the formula (A-I) and / or an amine compound represented by the formula (B-I) Is a polyimide resin containing.
  • the form in which the carboxylic acid anhydride or amide compound of the present invention is contained in the polyimide resin is usually such that the carboxylic acid anhydride or the amine compound is added to the main chain, side chain or terminal of the polyimide chain as described later.
  • This is a mode in which the organic group derived from the carboxylic anhydride of the present invention or the organic group derived from the amine compound of the present invention is incorporated as a part of the polymer chain.
  • a part of the carboxylic acid anhydride or amide compound of the present invention remains as a monomer or in the form of an oligomer.
  • Some forms may be incorporated into polyimide resin.
  • the term “comprising polyimide resin” is used in a sense that encompasses any of the above forms.
  • polyimide resin refers to a polymer having a polymer group in the polymer main chain, and encompasses polyimide, polyimide imide, and the like. Used in In addition, these polymers can be converted from imidized polyamic acid (or imidized precursors such as polyamic acid esters and polyisoimid). Polymers with various degrees of imidization exist up to the polyimide which has completely progressed, but these are also used to include these.
  • An acid anhydride other than the azo group-containing carboxylic acid anhydride of the present invention which is used as a raw material for producing the polyimide resin of the present invention.
  • Examples include tetracarboxylic dianhydride, tetracarboxylic acid esteri halide, trimethyl acetic anhydride or trimeric acid derivative, and acid trianhydride. is there.
  • Examples of the amide other than the amide compound of the present invention, which is used as a raw material for producing the polyimide resin of the present invention include diamin, triamine, and tetramine. Examples include lamin, or their isocyanate derivatives.
  • a polyimide precursor or a polyimide precursor in which imidization has partially progressed can be obtained. Generate and get polyimide from this.
  • trimellitic anhydride monohalide or trimellitic acid derivative
  • diamine or diisocynate
  • a polyamide can be obtained by reacting the amide compound of the formula (B-I) of the present invention with dicarboxylic dihalide.
  • tetracarboxylic acid Add dicarboxylic acid dihalide, etc. in addition to dianhydride, tetracarboxylic diester dihalide, trimeric trianhydride monohalide (or trimeric triacid derivative), and acid trianhydride They can also be used in combination of two or more.
  • Polyimide resins can also be produced by combining two or more diamines, triamines, tetraamines or their isolated derivatives.
  • the polyamic acid (or ester thereof) obtained by reacting the azo group-containing carboxylic anhydride of the general formula (A-III) of the present invention (or diester dihalide thereof) with diamine is as follows. Equation (P— 1)
  • Ar ′, Ar 2 and Ar represent an aromatic group which may have a substituent on the aromatic ring, and T represents a divalent organic group derived from a diamine compound. And P represent hydrogen or a monovalent organic group.
  • Ar ′, 1-2 and VIII represent an aromatic group which may have a substituent on an aromatic ring, and ⁇ represents a tetravalent organic compound derived from tetracarboxylic dianhydride. ⁇ represents hydrogen or a monovalent organic group, and X 2 and D have the same meanings as those in formula ( ⁇ —I).]
  • ⁇ represents a structural unit represented by the following formula: The converted polyimide is given by the following equation ( ⁇ — 4)
  • a compound having only one carboxylic anhydride group among azo group-containing carboxylic anhydrides represented by the general formula (A-I) is used.
  • a polyamic acid (or an ester thereof) obtained by reacting with an amine compound has the following formula (P-5)
  • a r ', A r 2, and A r 3' is, A r ', A r 2 and A r / is, P indicating an aromatic group have a substituent on the aromatic ring hydrogen Or a monovalent organic group.
  • the acid (or its ester) has the following formula ( ⁇ —7)
  • a r 1, A r 2 and A r ⁇ 'indicates an aromatic group have a substituent on the aromatic ring
  • Z is anhydrous Bok Li main Li Tsu Bokusanmata is derived derivatives thereof
  • P represents hydrogen or a monovalent organic group
  • X 2 and D have the same meanings as in formula (B-I).
  • the ring-closed (imidized) polyamide is represented by the following formula (P-8)
  • Tetracarboxylic dianhydrides that can be used include pyromellitic dianhydride,
  • tetracarboxylic diester dihalogenates examples include diester dihalides corresponding to the above tetracarboxylic dianhydrides. These include tetracarboxylic dianhydride and alcohol ( Or phenol) to give a tetracarboxylic diester (half ester), and then, for example, a reaction with thionyl chloride (in this case, the resulting product is tetracarboxylic diester dichloride). ) , Obtainable.
  • trimethyl citrate anhydride-halide or the trimethyl citrate derivative which can be used include trimethyl hydrate anhydride monochloride, trimethyl hydrate anhydride, and the like.
  • Trimethyl anhydride mononoride such as monofluoride, etc.
  • Trimethyl anhydride anhydrous such as 4-methoxyethoxycarbonylphthalic anhydride, 4-ethoxycarbonylphthalic anhydride Monocarboxylic acid triester, 4-Methoxycarbonizolef tazoleic acid, 4-ethoxycarbonisoleftasoleic acid, 2,5—Methyl dicarboxybenzoate, 2,5—Ethyl dicarboxybenzoate, 2,4 -Methisole dicarboxybenzoate, 2, 4- 4-Ethyl dicarboxybenzoate, etc., monoesters of trimethyl citrate, dimethyl 4-carboxyphthalate, getyl 4-carboxyphthalate, etc.
  • Acid trianhydrides that can be used include:
  • Glycerin tris trimethyl citrate monoester acid anhydride
  • trimethylolethane trimethyl citrate monoester acid anhydrous
  • Trimethylolpropane (trimeritic acid monoester anhydride),
  • 1,2,6-hexatrione monoester (trimellitic acid monoester anhydride),
  • trihydroxyacetophenone trimeritronic acid monoester anhydride
  • two or more kinds may be used in combination.
  • dicarboxylic acid dihalide examples include telerefonolinochloride,
  • Two or more types may be used in combination.
  • silicondiamine examples include 1,3-bis (3-aminopropyl) 1-1,1,1-tetrafluorodisiloxane, 1,3-bis (3-amino) Propyl) 1,1,1—tetramethyldisiloxane, 1,3—bis (4-aminobutyl) 1-1,1,1-tetramethyldisiloxane and the like.
  • Jiamin may be the corresponding jisiang. Trims that can be used include:
  • Carboxylic anhydride of the present invention [Carbonic anhydride of formula (A-I)]
  • the carboxylic acid of the present invention as a raw material is used.
  • the compound (bl) is added to the reaction vessel at the same time and mixed. ⁇ The reaction may be performed, or the acid anhydride (al) and the amine compound (bl) may be added first and mixed. After the reaction, the acid anhydride (a 2) or the amide compound (b 2) can be added and mixed and reacted.
  • the carboxylic acid anhydride (a 2) of the present invention contains only one carboxylic acid anhydride group
  • the tetracarboxylic acid dianhydride (a 2) is used rather than added simultaneously.
  • the molecular weight of the polyimide resin can be increased.
  • the amide conjugate (b 2) of the present invention contains only one amino group
  • Add dianhydride (al) and amide compound (bl) mix and reverse, and add this amide compound (b2) to increase the molecular weight of the polyimide resin. be able to.
  • the amount of the monomer used is 0.7 to 1.3 equivalents of the acid anhydride of the acid anhydride component (a1 + a2) with respect to the amine group of the amine component (bl + b2). It is preferably from 0.8 to 1.2 equivalents, more preferably from 0.9 to 1.1 equivalents. If the amount of (al + a2) is less than 0.7 equivalent or more than 1.3 equivalent, The resulting polyimide has a lower molecular weight.
  • the amount of the azo group-containing carboxylic acid anhydride (a 2) is determined when the azo group-containing carboxylic acid anhydride is a carboxylic acid anhydride containing two carboxylic acid anhydride groups. It can be 0 to 100 mol% of (a1 + a2). When used as a liquid crystal alignment film, the content is preferably 5 to 100 mol%.
  • ⁇ zone group-containing carboxylic acid anhydride is one that contains only one carboxylic acid anhydride group, 0-5 0 Monore 0/0 of the acid anhydride component (a 1 + a 2), Shi preferred Ku is from 1 to 4 0 mole 0/0. If it exceeds 50 mol%, the molecular weight of the obtained polyimide becomes low, and it is difficult to obtain a polyimide having uniform properties.
  • the amount of the amide compound (b 2) can be 0 to 100 mol% of the amide component (bl + b 2).
  • the content is preferably 5 to 100 mol%. If it is A Mi Roh casting based on a contained only one is ⁇ Mi emission component (bl + b 2) 0 to 5 0 mole 0/0, preferred and rather is 1-4 0 mol%. If it exceeds 50 mol%, the molecular weight of the resulting polyimide will be low, and it will be difficult to obtain a polyimide having uniform properties.
  • the molecular weight can be relatively increased.
  • silicondiamine When silicondiamine is used as a part of the diamine, 0.1 to 1 mol of the total amount of the diamine (b1 + b2) (100 mol%) is used. It is preferred to use 0 mol%.
  • the degree of imidization can be appropriately adjusted.
  • a catalyst such as tributylamine, triethylamine, triphenyl phosphite, etc.
  • reaction in the presence of from 0 to 15% by weight, preferably from 0.01 to 15% by weight, based on the total amount of the reactants, to achieve complete or almost complete reaction. It is possible to manufacture a polyimide that has been converted into a medium.
  • the above-mentioned polyamide acid or the precursor of the polyimide which has partially undergone imidization is further heated to 100 ° C. or more, especially 120 ° C. or more, and imidized.
  • an acid anhydride such as acetic anhydride, propionic anhydride or benzoic anhydride, a ring closing agent such as dicyclohexyl carpoimide or the like, and, if necessary, pyridine or isoquino.
  • Chemical ring closure (imidation) in the presence of a catalyst such as phosphorus, trimethylamine, aminoviridine, imidazole, etc. It is preferable to use 1 to 8 moles per 1 mole of the acid anhydride.
  • the method can produce a polyimide with almost or completely complete imidization. .
  • polyisoimid By appropriately selecting a ring-closing agent and a ring-closing catalyst, polyisoimid can be produced. By heating the obtained polyisoimid or partially imidized polyisoimid, the imidization was further promoted to completely imidize the polyisoimid. It can be polyimide.
  • organic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide and N—.
  • organic polar solvents include N, N-dimethylformamide, N, N-dimethylacetamide and N—.
  • organic polar solvents include N, N-dimethylformamide, N, N-dimethylacetamide and N—.
  • methyl-2-pyrrolidone dimethylsulfoxide, hexamethylphosphoramide, phenosol, m-cresol, chlorbenzen, etc.If they are compatible with each other, two or more are mixed. You can use it.
  • liquid crystal alignment film When a film of the polyimide resin obtained by the present invention is formed on a substrate having electrodes and treated by a known method such as rubbing, a liquid crystal alignment film can be obtained (rubbing). Liquid crystal alignment film).
  • the polyimide resin obtained in the present invention has a liquid crystal alignment ability by irradiating the film with linearly polarized light instead of the above rubbing treatment, and the liquid crystal alignment ability is stably held and fixed.
  • a rubbingless liquid crystal alignment film When the polyimide resin obtained in the present invention is used as a rubbingless liquid crystal orientation film, it can be thermoset (imidized) as necessary.
  • the thermosetting step of the polyimide resin can be performed simultaneously with the irradiation of the linearly polarized light, or can be performed within a long time after the irradiation of the linearly polarized light.
  • the liquid crystal alignment ability is retained in the polyimide resin film.
  • the reason for the fixation is considered as follows.
  • the functional groups of a single commander molecule ie, photoisomerizable and dichroic functional groups
  • the functional groups of a single commander molecule are incorporated as structural units of a relatively rigid resin.
  • photoisomerizable means that a photochemical reaction that changes the molecular structure by absorbing light occurs.
  • Dichroism refers to the ability to absorb light. Means different properties depending on the direction of the electric field vector of polarized light, and the “commander molecule” means a structural unit that is photoisomerizable and exhibits dichroism.
  • the liquid crystal alignment film using the polyimide resin of the present invention can be manufactured by applying and coating a liquid material or by a molding method.
  • Electrodes are formed on at least one of the paired substrates.
  • a transparent electrode such as IT0 (IndiumTinOxide) or a metal electrode can be used.
  • At least one of the pair of substrates uses a transparent substrate, and the transparent substrate includes a glass substrate, a plastic substrate, and a film-like substrate.
  • the transparent substrate includes a glass substrate, a plastic substrate, and a film-like substrate.
  • a substrate or the like can be used.
  • the transparent substrate a substrate that transmits a specific spectrum can be used. It is not necessary that the substrate be colorless and transparent. A transparent substrate or the like that transmits a specific polarized light can be used.
  • the liquid crystal alignment film using the polyimide resin of the present invention can be formed on at least one of the substrates.
  • the liquid crystal alignment film using the polyimide resin of the present invention can have liquid crystal alignment ability by a method such as a rubbing method.
  • a method such as a rubbing method.
  • liquid crystal alignment ability can be provided.
  • a part of the liquid crystal alignment film is irradiated with linearly polarized light so as to have liquid crystal alignment capability, and the other portion is provided with a liquid crystal alignment capability by a method such as a rubbing method.
  • a liquid crystal display device having a liquid crystal holding substrate can be obtained by a known method using the liquid crystal holding substrate.
  • the operation mode of the liquid crystal display element is TN (high-density dronematic), S-throat (snoo-twisted rhematic), or IPS (in-plane switch). Is also good.
  • the liquid crystal used for the liquid crystal display element may be a nematic liquid crystal or a ferroelectric liquid crystal (a ferric liquid crystal liquid; FLC), and may be an antiferroelectric liquid crystal.
  • Liquid crystal Anti-Electric Liquid Liquid Crystal; AFLC).
  • the insoluble portion was collected by suction filtration (the insoluble portion was washed three times with 3 ml of acetic anhydride), transferred to a 500 ml Nilo flask equipped with a reflux condenser, and dehydrated with 34 O ml of toluene. Was added and the mixture was refluxed for 20 minutes. After cooling to room temperature, the insoluble part was filtered by suction, and 4-[3,4- (Dicarboxy-rich hydride) benzoyl] oxyl 2-Hydroxy [(4-nitrophenyl) azo] benzene [Formula (A-Ia1)] 5 g (58%) was obtained.
  • Infrared absorption spectrum (KBr tablet method): 3416, 1848, 178, 170, 168, 166, 164, 168, 1590, 1560, 1520, 1510, 1482, 1460, 1424, 1388, 1340, 1266. 1 2 2 2, 1 1 8 2, 1 1 6 2, 1 1 0 6, 1 0 9 8, 1 0 5 4, 9 9 6, 9 6 4, 9 1 2, 8 9 2, 8 5 6, 8 20, 75 2, 71 2, 70 0, 68 4, 65 4, 64 24 608, 58 86, 54 48, 52 22 cm — 1
  • Example 2 A 100 ml three-neck flask equipped with a reflux condenser was charged with the 4- [3,4- (dicarboxy-rich-anhydride) benzoyl] oxyl-2 obtained in Example 1. Hydroxy [(412-Trophenyl) azo] Weigh 3 g (7 mm 01) of benzene, dry under an argon atmosphere N, N-dimethylformamide 23 m 1 and pyridine 1.7 ml (21 mmo 1) were added. After heating the mixture at 50 ° C., 2 ml (21 mmol) of acetic anhydride was added dropwise thereto.
  • the precipitated crystals were filtered by suction, washed with acetic anhydride (8 ml ⁇ 2 times), and dried under reduced pressure at 0.5 Torr for 2 hours. This solid was transferred to a 500 ml Niloflasco equipped with a reflux condenser, and 70 O ml of dehydrated toluene was added thereto, followed by heating at 110 ° C for 12 minutes.
  • Phase transition point 196 ° C, 247 ° C
  • Infrared absorption spectra (KBr tablet method): 34 08, 33 32, 32 08, 30 32, 29 28, 15 98, 15 58, 1 4 9 8, 1 4 5 0, 1 4 1 4, 1 3 7 4, 1 3 0 0, 1 2 2 2, 1 1 4 0, 1 0 6 4, 9 3 8, 8 3 6, 7 6 2, 6 8 4, 5 4 8, 4 2 0 cm — '
  • DMF dimethylformamide
  • the weight average molecular weight of the obtained polymer was 44.6 k, and the degree of dispersion (weight average molecular weight / number average molecular weight) was 1.58.
  • the glass transition point of the cured product of the obtained polymer was 16 ° C.
  • the weight average molecular weight and the degree of dispersion of the polymer were determined in terms of polystyrene using GPC.
  • N-methisolate 2 Pyrolidone 7 g
  • 1 (2,4-diaminophenol) 1 2-[4-(phenylazo) phenoxy]-ethane 0.139 g (0.4 millimol)
  • 4, 4 '-diaminodiphenyl methane 0 .317 g (1.6 mmol) was added and stirred until a homogeneous solution was obtained.
  • 0.64 4 g (2 millimoles) of 3,4,3 ', 4'-benzophenenotetracarboxylic dianhydride was added little by little.
  • the reaction was carried out for 5 hours while cooling in an ice bath to obtain a polyamic acid solution.
  • the weight average molecular weight of the obtained polymer was 103.5 k, and the degree of dispersion was 1.94.
  • the glass transition point of the obtained cured product of the polymer was 250 ° C. gQ
  • N-methyl-2-pyrrolidone 23 mL, 10 mL of a 3-neck flask equipped with a thermometer, stirrer, drying tube and nitrogen inlet tube, N-methyl-2-pyrrolidone 1.llg (10.2 mmol) and stirred until a homogeneous solution was obtained.
  • N-methyl-2-pyrrolidone 4.66 g, 4- [2— (2,4-diaminopheno). 0.29 g (1.24 mimol) of xy) ethoxy] stilbene and 0.245 g (1.24 mimol) of 4,4'-diaminodidiphenylmethane ) was added and stirred until a homogeneous solution was obtained. Then, while cooling in an ice bath, add 0.526 g (2.48 millimoles) of tetrahydrofuran-1,2,3,4,5-tetracarboxylic dianhydride. Was added in small portions.
  • the mixture was reacted for 7 hours while cooling in an ice bath to obtain a solution of polyamide acid.
  • the weight average molecular weight of the obtained polymer was 60.3 k, and the Was 2.52.
  • the glass transition point of the obtained cured product of the polymer was 23.degree. C.
  • N-methyl-1-pyrrolidone 4.66 g, 1- (2,4-diaminophenol).
  • N-methyl-2-pyrrolidone 4.66 g, 1- (2,4-diamisopheno).
  • 2-[4-(phenylazo) phenoxy]-ethane 0.459 g (1.32 mmol) was added and stirred until a homogeneous solution was obtained.
  • 4-(phenylazo) resorcinol 0.741 g (1.332 millimoles) of rubis (trimethyl nitric anhydride) was added in small portions.
  • the mixture was reacted for 6 and a half hours while cooling in an ice bath to obtain a solution of polyamide acid.
  • the weight average molecular weight of the obtained polymer was 46.0 k, and the dispersity was 1.84.
  • the glass transition point of the cured product of the obtained polymer was 158 ° C.
  • the mixture was reacted for 6 hours and 20 minutes while cooling in an ice bath to obtain a solution of polyamide acid.
  • the weight average molecular weight of the obtained polymer was 144 k, and the dispersity was 2.74.
  • the glass transition point of the obtained cured product of the polymer was 204 ° C.
  • N-methyl-1-pyrrolidone 4.66 g, 2,4—diamino azobenzene 0.3 1 lg ( 1.4.7 (Mol) and stirred until a homogeneous solution was obtained. Then, while cooling in an ice bath, add 0.889 g (1.46 millimoles) of 41- (phenylazo) resorcinol bis (trimellitic anhydride) in small portions. did. After completion of the addition, the mixture was reacted for 9 hours while cooling in an ice bath to obtain a polyamic acid solution. The weight average molecular weight of the obtained polymer was 30.1 k, and the degree of dispersion was 1.65.
  • Example 10 The polyamic acid obtained in Example 10 was diluted with N, N-dimethyl acetate amide to a solid content of about 5% by weight to prepare a composition for a liquid crystal alignment film. A solution of this composition was spin-coated on two glass substrates with ITO transparent electrodes and heated at 70 ° C. for 1 minute to evaporate the solvent to form a resin film on the substrate.
  • a high-pressure mercury lamp was used as a light source for polarized light irradiation, and the amount of radiation near the wavelength of 420 nm transmitted through the polarizing film was approximately 10 nm from a direction almost perpendicular to the glass substrate surface through the polarizing film. Irradiation was performed so as to be J / cm 2 . After cooling the substrate, the resin coating layers are combined to face each other so that the direction of the polarization axis is parallel, and the periphery is sealed with an epoxy-based sealant, so that the gap is about 5 ⁇ m. Thus, a test liquid crystal display cell was assembled.
  • liquid crystal display cell a liquid crystal ZLI 1 4 7 9 2 (Trade name, manufactured by Merck & Co.) was sealed at room temperature to form a liquid crystal cell, and good alignment was obtained. About three months later, when this liquid crystal cell was observed again, it was found that it had maintained a good orientation.
  • the polyamide acid obtained in Example 11 was diluted with N-methyl-2-pyrrolidone to a solid content of about 5% by weight to prepare a composition for a liquid crystal alignment film.
  • a solution of this composition was spin-coated on two glass substrates with ITO transparent electrodes, and heated at 70 ° C. for 1 minute to evaporate the solvent to form a resin film on the substrate.
  • the substrates were combined with the resin coating layers facing each other, the periphery was sealed with an epoxy sealant, and a test liquid crystal display cell was assembled so that the gap was about 25 ⁇ m.
  • a high-pressure mercury lamp was used as the light source for irradiating the polarized light. Irradiation was performed so as to be 10 J / cm 2 .
  • a liquid crystal ZLI-47992 (trade name, manufactured by Merck) was sealed in the test liquid crystal display cell at room temperature to form a liquid crystal cell, and good alignment was obtained. About three months later, when this liquid crystal cell was observed again, good alignment was maintained.
  • Application example 3
  • Example 12 The polyamic acid obtained in Example 12 was diluted with N-methyl-2-pyrrolidone so as to have a solid content of about 5% by weight to obtain a varnish for a liquid crystal alignment film.
  • the varnish was applied onto two glass substrates with IT transparent electrodes with a spinner, ripened at 70 ° C. for 1 minute to evaporate the solvent, and a resin film was formed on the substrates.
  • test liquid crystal display cell was assembled such that A liquid crystal ZLI-14792 (trade name, manufactured by Merck) was sealed in the test liquid crystal display cell at room temperature, and a good alignment was obtained when the liquid crystal cell was formed.
  • Example 15 The polyamic acid obtained in Example 15 was diluted with N-methyl-2-pyrrolidone to a solid content of about 5% by weight to prepare a composition for a liquid crystal alignment film.
  • a solution of this composition was spinner-coated on two glass substrates with ITO transparent electrodes. The solvent was evaporated by heating at 1 ° C for 1 minute to form a resin film on the substrate. These glass substrates are combined with the resin coating layer facing each other, and the periphery is sealed with an epoxy sealant leaving the liquid crystal injection port, and the test is performed so that the gap is about 25 / m. Assembled empty cells.
  • a microwave-excited electrodeless lamp (Hyujon AEL-1B / M) was used as the light source for polarized light irradiation.
  • An optical receiver (UV-42) with a peak sensitivity of 42 O nm was applied almost perpendicularly to the test empty cell placed on a stainless steel plate through a polarizing film containing an ultraviolet absorber.
  • Ritsu digit in a luminometer to measure (Oak Co. UV-M 0 2) illumination, polarized illumination in earthenware pots by the amount of irradiation is 9 J / cm 2.
  • liquid crystal ZLI-4792 (trade name, manufactured by Merck) was sealed at room temperature, and the liquid crystal injection port was sealed with an epoxy sealant to form a liquid crystal cell. Good orientation was obtained for the rollers.
  • the azo group-containing carboxylic anhydride according to claims 1 to 3 is a novel compound, and is used as a raw material for producing a polyimide resin or as a material for a liquid crystal alignment film, particularly a rubbingless liquid crystal alignment film. Further, it is useful as a nonlinear optical material such as an optical waveguide and a wavelength conversion element. You.
  • the amide compound according to claims 4 to 6 is a novel compound, and is used as a raw material for producing a polyimide resin or as a material for a liquid crystal alignment film, particularly a Rabin-Gress liquid crystal alignment film, and furthermore, as an optical waveguide. It is useful as a nonlinear optical material such as a wavelength conversion element.
  • the azo group-containing rubonic anhydride of claims 1 to 3 can be produced.
  • the amide compound of claim 46 can be produced.
  • the polyimide resin according to claims 9 to 12 is useful as a material for a liquid crystal alignment film, particularly a rubbingless liquid crystal alignment film, and further as a non-linear optical material such as an optical waveguide and a wavelength conversion element.

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Abstract

L'invention porte sur des anhydrides azoïques de l'acide carboxylique de formule générale (A-Ia) et sur des composés aminés de formule générale (B-Ia) [dans lesquelles: L est hydrogène ou analogue; X2 est N ou CR3 (R3 étant hydrogène ou analogue); et n est un entier de 2 à 20]; et sur une résine de type polyimide comportant des anhydride d'acide et/ou des composés aminés, utilisables comme film antifriction à alignement de cristaux liquides.
PCT/JP1996/001887 1995-07-06 1996-07-08 Nouveaux anhydrides de l'acide carboxylique, composes amines, resines polyimides, et leur procede de fabrication WO1997002233A1 (fr)

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JP2013120207A (ja) * 2011-12-06 2013-06-17 Nissan Chem Ind Ltd 新規ジカルボン酸無水物及び製造法、液晶配向処理剤、液晶配向膜、及びそれを用いた液晶表示素子
JP5888246B2 (ja) * 2011-01-28 2016-03-16 三菱化学株式会社 ２−フルアルデヒドの製造方法

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JPH05214101A (ja) * 1992-02-06 1993-08-24 Hitachi Ltd 熱可塑型ポリエステルイミドとそれを用いた電子部品および電子装置
JPH0643465A (ja) * 1992-07-24 1994-02-18 Hitachi Chem Co Ltd 液晶配向膜，これを有する液晶挟持基板及び液晶表示素子
JPH0812759A (ja) * 1994-04-28 1996-01-16 Nissan Chem Ind Ltd 新規なジアミノベンゼン誘導体及びそれを用いたポリイミド
JPH0848772A (ja) * 1994-08-03 1996-02-20 Chisso Corp 液晶基を有するポリイミド

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US3597392A (en) * 1969-01-21 1971-08-03 Monsanto Co Functionally substituted highly ordered azo-aromatic polyimides
JPH03250028A (ja) * 1990-02-28 1991-11-07 Japan Carlit Co Ltd:The 新規ポリイミド
JPH05214101A (ja) * 1992-02-06 1993-08-24 Hitachi Ltd 熱可塑型ポリエステルイミドとそれを用いた電子部品および電子装置
JPH0643465A (ja) * 1992-07-24 1994-02-18 Hitachi Chem Co Ltd 液晶配向膜，これを有する液晶挟持基板及び液晶表示素子
JPH0812759A (ja) * 1994-04-28 1996-01-16 Nissan Chem Ind Ltd 新規なジアミノベンゼン誘導体及びそれを用いたポリイミド
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JP5888246B2 (ja) * 2011-01-28 2016-03-16 三菱化学株式会社 ２−フルアルデヒドの製造方法
JP2016102133A (ja) * 2011-01-28 2016-06-02 三菱化学株式会社 ２−フルアルデヒドの製造方法
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JP2013120207A (ja) * 2011-12-06 2013-06-17 Nissan Chem Ind Ltd 新規ジカルボン酸無水物及び製造法、液晶配向処理剤、液晶配向膜、及びそれを用いた液晶表示素子

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